You are on page 1of 470

Chemical and Isotopic Groundwater Hydrology

Third Edition

Emanuel Mazor
Weizmann Institute of Science Rehovot, Israel





This edition is updated and expanded from a portion of the second edition (Chemical and Isotopic Groundwater Hydrology: The Applied Approach, Marcel Dekker, 1997). The remaining material in the second edition has been adapted and expanded for Hydrology of Oceans, Formation Waters, and Petroleum Deposits (Marcel Dekker, Inc., in press). Although great care has been taken to provide accurate and current information, neither the author(s) nor the publisher, nor anyone else associated with this publication, shall be liable for any loss, damage, or liability directly or indirectly caused or alleged to be caused by this book. The material contained herein is not intended to provide specic advice or recommendations for any specic situation. Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only for identication and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress. ISBN: 0-8247-4704-6 This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc., 270 Madison Avenue, New York, NY 10016, U.S.A. tel: 212-696-9000; fax: 212-685-4540 Distribution and Customer Service Marcel Dekker, Inc., Cimarron Road, Monticello, New York 12701, U.S.A. tel: 800-228-1160; fax: 845-796-1772 Eastern Hemisphere Distribution Marcel Dekker AG, Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-260-6300; fax: 41-61-260-6333 World Wide Web The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales/Professional Marketing at the headquarters address above. Copyright # 2004 by Marcel Dekker, Inc. All Rights Reserved. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microlming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): 10 9 8 7 6 5 4 3 2 1 PRINTED IN THE UNITED STATES OF AMERICA


Editorial Board
Agricultural Engineering Animal Science Crops Irrigation and Hydrology Microbiology Plants Robert M. Peart, University of Florida, Grainesville Harold Hafs, Rutgers University, New B~mswick, New Jersey Mohammad Pessarakli, University of Anzona, Tucson Donald R. Nielsen, University of California, Davis Jan Dirk van Elsas, Research Institute for Plant Protection, Wageningen, The Netherlands L. David Kuykendall, U.S. Department of Agriculture, Beltsville, Maryland Kenneth B. Marcum, Texas A&M University, El Paso, Texas Jean-Marc Bollag, Pennsylvania State University, University Park, Pennsylvania Tsuyoshi Miyazaki, University of Tokyo


Soil Biochemistry, Soil Biochemistry, Soil Biochemistry, Soil Biochemistry, Soil Biochemistry, Soil Biochemistry, Soil Biochemistry, Soil Biochemistry, Soil Biochemistry, Soil Biochemistry,

Volume 7, edited by A. D. McLaren and G. H. Peterson Volume 2, edited by A. D. McLaren and J. SkujinS Volume 3, edited by E. A. Paul and A. D. McLaren Volume 4, edited by E. A. Paul and A. D. McLaren Volume 5, edited by E. A. Paul and J. N. Ladd Volume 6, edited by Jean-Marc Bollag and G. Stotzky Volume 7, edited by G. Stotzky and Jean-Marc: Bollag Volume 8, edited by Jean-Marc Bollag and G. Stotzky Volume 9, edited by G. Stotzky and Jean-Marc: Bollag Volume 70, edited by Jean-Marc Bollag and G. Stotzky

Organic Chemicals in the Soil Environment, Volumes 7 and 2, edited by C. A. I. Goring and J. W. Hamaker Humic Substances in the Environment, M. Schnitzer and S. U. Khan Microbial Life in the Soil: An lntroduction, T. Hattori Principles of Soil Chemistry, Kim H. Tan Soil Analysis: lnstrumental Techniques and Related Procedures, edited by Keith A. Smith Soil Reclamation Processes: Microbiological Analyses and Applications, edited by Robert L. Tate Ill and Donald A. Klein Symbiotic Nitrogen Fixation Technology, edited by Gerald H. Elkan

Soil- Water Interactions: Mechanisms and Applications, Shingo lwata and Toshio Tabuchi with Benno P. Warkentin Soil Analysis: Modern lnstrumental Techniques, Second Edition, edited by Keith A. Smith Soil Analysis: Physical Methods, edited by Keith A. Smith and Chris E. Mullins Growth and Mineral Nutrition of Field Crops, N. K. Fageria, V. C. Baligar, and Charles Allan Jones Semiarid Lands and Deserts: Soil Resource and Reclamation, edited by J. SkujinS Plant Roots: The Hidden Half, edited by Yoav Waisel, Amram Eshel, and Uzi Kafkafi Plant Biochemical Regulators, edited by Harold W. Gausman Maximizing Crop Yields, N. K. Fageria Transgenic Plants: Fundamentals and Applications, edited by Andrew Hiatt Soil Microbial Ecology: Applications in Agricultural and Environmental Management, edited by F. Blaine Metting, Jr. Principles of Soil Chemistry: Second Edition, Kim H. Tan Water Flow in Soils, edited by Tsuyoshi Miyazaki Handbook of Plant and Crop Stress, edited by Mohammad Pessarakli Genetic lmprovement of Field Crops, edited by Gustavo A. Slafer Agricultural Field Experiments: Design and Analysis, Roger G. Petersen Environmental Soil Science, Kim H. Tan Mechanisms of Plant Growth and Improved Productivity: Modern Approaches, edited by Amarjit S. Basra Selenium in the Environment, edited by W. T. Frankenberger, Jr., and Sally Benson Plant-Environment Interactions, edited by Robert E. Wilkinson Handbook of Plant and Crop Physiology, edited by Mohammad Pessarakli Handbook of Phyfoalexin Metabolism and Action, edited by M. Daniel and R. P. Purkayastha Soil- Water Interactions; Mechanisms and Applications, Second Edition, Revised and Expanded, Shingo lwata, Toshio Tabuchi, and Benno P. W arkentin Stored-Grain Ecosystems, edited by Digvir S. Jayas, Noel D. G. White, and William E. Muir Agrochemicals from Natural Products, edited by C. R. A. Godfrey Seed Development and Germination, edited by Jaime Kigel and Gad Galili Nitrogen Fertilization in the Environment, edited by Peter Edward Bacon Phyfohormones in Soils: Microbial Production and Function, William T. Frankenberger, Jr., and Muhammad Arshad Handbook of Weed Management Systems, edited by Albert E. Smith Soil Sampling, Preparation, and Analysis, Kim H. Tan Soil Erosion, Conservation, and Rehabilitation, edited by Menachem Agassi Plant Roots: The Hidden Half, Second Edition, Revised and Expanded, edited by Yoav Waisel, Amram Eshel, and Uzi Kafkafi Photoassimilate Distribution in Plants and Crops: Source-Sink Relationships, edited by Eli Zamski and Arthur A. Schaffer

Mass Spectrometry of Soils, edited by Thomas W. Boutton and Shinichi Y amasaki Handbook of Photosynthesis, edited by Mohammad Pessarakli Chemical and lsotopic Groundwater Hydrology: The Applied Approach, Second Edition, Revised and Expanded, Emanuel Mazor Fauna in Soil Ecosystems: Recycling Processes, Nutrient Fluxes, and Agricultural Production, edited by Gero Benckiser Soil and Plant Analysis in Sustainable Agriculture and Environment, edited by Teresa Hood and J. Benton Jones, Jr. Seeds Handbook: Biology, Production, Processing, and Storage, B. B. Desai, P. M. Kotecha, and D. K. Salunkhe Modern Soil Microbiology, edited by J. D. van Elsas, J. T. Trevors, and E. M. H. Wellington Growth and Mineral Nutrition of Field Crops: Second Edition, N. K. Fageria, V. C. Baligar, and Charles Allan Jones Fungal Pathogenesis in Plants and Crops: Molecular Biology and Host Defense Mechanisms, P. Vidhyasekaran Plant Pathogen Detection and Disease Diagnosis, P. Narayanasamy Agricultural Systems Modeling and Simulation, edited by Robert M. Peart and R. Bruce Curry Agricultural Biotechnology, edited by Arie Altman Plant-Microbe Interactions and Biological Control, edited by Greg J. Boland and L. David Kuykendall Handbook of Soil Conditioners: Substances That Enhance the Physical Properties of Soil, edited by Arthur Wallace and Richard E. Terry Environmental Chemistry of Selenium, edited by William T. Frankenberger, Jr., and Richard A. Engberg Principles of Soil Chemistry: Third Edition, Revised and Expanded, Kim H. Tan Sulfur in the Environment, edited by Douglas G. Maynard Soil-Machine Interactions: A Finite Element Perspective, edited by Jie Shen and Radhey La1 Kushwaha Mycotoxins in Agriculture and Food Safety, edited by Kaushal K. Sinha and Deepak Bhatnagar Plant Amino Acids: Biochemistry and Biotechnology, edited by Bijay K. Singh Handbook of Functional Plant Ecology, edited by Francisco I. Pugnaire and Fernando Valladares Handbook of Plant and Crop Stress: Second Edition, Revised and Expanded, edited by Mohammad Pessarakli Plant Responses to Environmental Stresses: From Phytohormones to Genome Reorganization, edited by H. R. Lerner Handbook of Pest Management, edited by John R. Ruberson Environmental Soil Science: Second Edition, Revised and Expanded, Kim H. Tan Microbial Endophytes, edited by Charles W. Bacon and James F. White, Jr. Plant-Environment Interactions: Second Edition, edited by Robert E. W ilkinson Microbial Pest Control, Sushi1 K. Khetan

Soil and Environmental Analysis: Physical Methods, Second Editicm, Revised and Expanded, edited by Keith A. Smith and Chris E. Mullins The Rhizosphere: Biochemistry and Organic Substances at the Soil-Plant Interface, Roberto Pinton, Zen0 Varanini, and Paolo Nannipieri Woody Plants and Woody Plant Management: Ecology, Safety, and Environmental Impact, Rodney W. Bovey Metals in the Environment: Analysis by Biodiversity, M. N. V. Prasad Plant Pathogen Detection and Disease Diagnosis: Second Edition, li!evised and Expanded, P. Narayanasamy Handbook of Plant and Crop Physiology: Second Edition, Revised and Expanded, edited by Mohammad Pessarakli Environmental Chemistry of Arsenic, edited by William T. Frankenberger,Jr. Enzymes in the Environment: Activity, Ecology, and Applications, edited by Richard G. Burns and Richard P. Dick Plant Roots: The Hidden Half, Third Edition, Revised and Expanded, edited by Yoav Waisel, Amram Eshel, and Uzi Kafkafi Handbook of Plant Growth: pH as the Master Variable, edited by Zdenko Rengel Biological Control of Crop Diseases, edited by Samuel S. Gnanamanickam Pesticides in Agriculture and the Environment, edited by Willis B. Wheeler Mathematical Models of Crop Growth and Yield, Allen R. Overman and Richard V. Scholtz Ill Plant Biotechnology and Transgenic Plants, edited by Kirsi-Marja O \smanC . Caldentey and Wolfgang H. Barz Handbook of Postharvest Technology: Cereals, Fruits, Vegetables, Tea, and Spices, edited by Amalendu Chakraverty, Arun S. Mujumdar, G. S. Vijaya Raghavan, and Hosahalli S. Ramaswamy Handbook of Soil Acidity, edited by Zdenko Rengel Humic Matter in Soil and the Environment: Principles and Controversies, Kim H. Tan Molecular Host Resistance to Pests, S. Sadasivam and B. Thayumanavan Soil and Environmental Analysis: Modern lnstrumental Techniques, Third Edition, edited by Keith A. Smith and Malcolm S. Cresser Chemical and lsotopic Groundwater Hydrology: Third Edition, Ernanuel Mazor

Additional Volumes in Preparation

Agricultural Systems Management: Optimizing Efficiency and Performance, Robert M. Peart and Dean W. David Shoup Seeds Handbook: Biology, Production, Processing, and Storage, Second Edition, Revised and Expanded, Babasaheb B. Desai Physiology and Biotechnology Integration for Plant Breeding, edited by Henry T. Nguyen and Abraham Blum


Groundwater is a vital resource in steadily increasing demand by man, but man threatens its quality and mishandles the available quantity. In order to properly manage the resource, we have to study it in detail, recognize its properties, and understand its dynamicsin large-scale regions as well as in every locally studied system. Chemical and isotopic hydrology are tailored to these challenges, and the hydrochemist has a key role as a consultant to the groundwater developers and managers, decision-makers, and environmental quality authorities. This book provides the applied approach, incorporating maximum eld observations, and parameters measured in eld studies, enabling the reader to: (a) understand the natural regimes of groundwater systems in specic case study areas, (b) understand the consequences of anthropogenic intervention, (c) reach conclusions and recommendations related to management of the water resource, and (d) establish boundary conditions that lead to conceptual models. The book addresses these topics, emphasizes the processing of data, discusses over 100 published case studies, and preaches for independent interpretations. It is written with the assumption that most eld hydrologists bring their samples to specialized laboratories for analysis, and discusses the examination of data quality. The variety of physical, chemical, isotopic, and dating methods is systematically presented via the basic observations, stressing the applied aspects, based on the multiparametermultisampling approach.



This third edition of the book has been updated, and a new chapter addresses water quality standards, monitoring networks, data banks, and the important area of educational activities. Emanuel Mazor


Preface 1. IntroductionChemical and Isotopic Aspects of Hydrology 1.1 The Concealed Nature of Groundwater 1.2 Groundwater Composition 1.3 Information Encoded into Water During the Hydrological Cycle 1.4 Questions Asked 1.5 Phenomenological Conceptual Models and Mathematical Models 1.6 Economic Considerations of Field Hydrochemistry 1.7 Environmental Issues 1.8 Summary Exercises Physical and Geological Concepts Basic 2.1 2.2 2.3 2.4 2.5 2.6 2.7 Hydrological Concepts The Aerated Intake Zone The Saturated Zone and the Water Table Aquifers and Aquicludes Recharge Discharge Evapotranspiration Permeability, Impermeability, and the Selection of Representative Values

iii 1 1 1 3 5 7 8 10 11

Part I. 2.

13 13 15 16 19 19 20 21



2.8 2.9 2.10 2.11 2.12 2.13 2.14 2.15 2.16 2.17 2.18 3.

Through-Flow Systems: Unconned and Conned Karstic Systems: Paths of Preferred Flow Flow Velocity and Groundwater Age Flow of Water: Basic Observations Two Basic Experiments of Water Flow A Model of L-Shape Through-Flow Paths and Zones of Stagnation Deep Basin Compartments of Pressurized Water, Petroleum, and Geothermal Fluids The Traditional Model of U-Shape Flow Paths Discussion of the U-Shape Flow Paths Model Summary of Modes of Groundwater Flow Summary Exercises

24 27 28 31 32 34 42 43 45 48 48 50 50 52 55 55 58 59 59 65 66 66 68 74 75 77 78 80 84 89 89 94

Geological Data 3.1 Lithology and Its Bearing on Water Composition 3.2 Properties of Geological Materials and Their Bearing on Recharge and Groundwater Storage 3.3 Layering and Its Control on Groundwater Flow 3.4 Folded Structures and Their Bearing on Flow Direction, Connement, and Entrapment 3.5 Faults Controlling Groundwater Flow 3.6 Intrusive Bodies Inuencing Groundwater Flow 3.7 Hydrochemical and Isotopic Checks of Geological and Hydrological Models 3.8 Summary Exercises Physical Parameters 4.1 Water Table Measurements 4.2 Interpretation of Water Table Data 4.3 Gradient and Flow Direction 4.4 The Need for Complementing Data to Check Deduced Gradients and Flow Directions 4.5 Velocities and Pumping Tests 4.6 Chemical and Physical Measurements During Pumping Tests 4.7 Temperature Measurements 4.8 Tracing Groundwater by TemperatureA Few Case Studies: The Mohawk River 4.9 Cold and Hot Groundwater Systems 4.10 Discharge Measurements and Their Interpretative Value 4.11 Summary Exercises




Part II. 5.

Chemical Tools of Groundwater Hydrology Elements, Isotopes, Ions, Units, and Errors 5.1 Elements 5.2 Isotopes 5.3 Atomic Weight 5.4 Ions and Valences 5.5 Ionic Compounds 5.6 Concentration Units 5.7 Reproducibility, Accuracy, Resolution, and Limit of Detection 5.8 Errors and Signicant Figures 5.9 Checking the Laboratory 5.10 Evaluation of Data Quality by Data Processing Techniques 5.11 Putting Life into a Dry Table 5.12 Evaluation of Calculated Reproducibilities and Reaction Errors 5.13 Summary Exercises Chemical Parameters: Data Processing 6.1 Data Tables 6.2 Fingerprint Diagrams 6.3 Composition Diagrams 6.4 Major Patterns Seen in Composition Diagrams 6.5 Establishing Hydraulic Interconnections 6.6 Mixing Patterns 6.7 End Member Properties and Mixing Percentages 6.8 WaterRock Interactions and the Types of Rocks Passed 6.9 Water Composition: Modes of Description 6.10 Compositional Time Series 6.11 Some Case Studies 6.12 Saturation and Undersaturation with Regard to Halite and Gypsum: The Hydrochemical Implications 6.13 Sea-Derived (Airborne) Ions: A Case Study Demonstrating the Phenomenon 6.14 Sources of Chlorine in Groundwater 6.15 Evapotranspiration Index: Calculation Based on Chlorine as a Hydrochemical Marker 6.16 CO2-Induced WaterRock Interactions Revealed by Chlorine Serving as a Hydrochemical Marker 6.17 Summary Exercises 97 97 98 99 100 101 101 102 104 105 107 108 112 113 114 114 115 121 122 125 129 132 136 138 139 141 145 147 149 150 151 152





Planning Hydrochemical Studies 7.1 Representative Samples 7.2 Data Collection During Drilling 7.3 Depth Proles 7.4 Data Collection During Pumping Tests 7.5 Importance of Historical Data 7.6 Repeated Observations, or Time-Data Series 7.7 Search for Meaningful Parameters 7.8 Sampling for Contour Maps 7.9 Sampling Along Transects 7.10 Reconnaissance Studies 7.11 Detailed Studies 7.12 Pollution-Related Studies 7.13 Summary: A Planning List 7.14 Summary Exercises Chemical Parameters: Field Work 8.1 Field Measurements 8.2 Smell and Taste 8.3 Temperature 8.4 Electrical Conductance 8.5 pH 8.6 Dissolved Oxygen 8.7 Alkalinity 8.8 Sampling for Dissolved Ion Analyses 8.9 Sampling for Isotopic Measurements 8.10 Preservation of Samples 8.11 Eforescences 8.12 Equipment List for Field Work

156 156 158 160 161 161 162 163 164 165 165 166 166 167 168 170 170 171 172 172 173 174 176 176 177 178 178 179


Part III. 9.

Isotopic Tools of Groundwater Hydrology: Water Identication and Dating Hydrogen and Oxygen Isotopes Isotopic Composition of Water Molecules Units of Isotopic Composition of Water Isotopic Fractionation During Evaporation and Some Hydrological Applications The Meteoric Isotope Line Temperature Effect Amount Effect Continental Effect Altitude Effect 181 181 182 182 185 189 190 193 194

Stable 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8



9.9 9.10 9.11 9.12 9.13 10.

Tracing Groundwater with Deuterium and 18O: Local Studies Tracing Groundwater with Deuterium and 18O: A Regional Study The Need for Multisampling Sample Collection for Stable Hydrogen and Oxygen Isotopes and Contact with Relevant Laboratories Summary Exercises

198 202 206 208 208 210 210 211 212 216 217

Tritium Dating 10.1 The Radioactive Heavy Hydrogen Isotope 10.2 Natural Tritium Production 10.3 Manmade Tritium Inputs 10.4 Tritium as a Short-Term Age Indicator 10.5 Tritium as a Tracer of Recharge and Piston Flow: Observations in Wells 10.6 The Special Role of Tritium in Tracing Intermixing of Old and Recent Waters and Calculation of the Extrapolated Properties of the End Members 10.7 Tritium, Dissolved Ions, and Stable Isotopes as Tracers for Rapid Discharge Along Fractures: The Mont Blanc Tunnel Case Study 10.8 The Tritium-3He Groundwater Dating Method 10.9 Sample Collection for Tritium Measurements 10.10 Summary Exercises Radiocarbon Dating 11.1 The Isotopes of Carbon 11.2 Natural 14C Production 11.3 Manmade 14C Dilution and Addition 11.4 14C in Groundwater: An Introduction to Groundwater Dating 11.5 Lowering of 14C Content by Reactions with Rocks 11.6 13C Abundances and Their Relevance to 14C Dating of Groundwater 11.7 Application of d13C to Correct Observed 14C Values for Changes Caused by Interactions with Carbonate Rocks 11.8 Direction of Down-Gradient Flow and Groundwater Age Studied by 14C: Case Studies 11.9 Flow Discontinuities Between Adjacent Phreatic and Conned Aquifers Indicated by 14C and Other Parameters


225 229 230 230 231 231 231 233 233 237 238


241 243



11.10 Mixing of Groundwaters Revealed by Joint Interpretation of Tritium and 14C Data 11.11 Piston Flow Versus Karstic Flow Revealed by 14C Data 11.12 Sample Collection for 14C and 13C Analyses and Contact with Relevant Laboratories 11.13 Summary Exercises 12. Chlorine-36 Dating 12.1 The Radioactive Isotope of Chlorine and Its Production 12.2 A Potential Tool for Groundwater Dating 12.3 Processes Controlling the 36Cl Concentration in Groundwater 12.4 Groundwater Dating by 36Cl 12.5 A Number of Case Studies 12.6 Summary 12.7 Summary Exercises The Noble Gases 13.1 Rare, Inert, or Noble? 13.2 Atmospheric Noble Gases and Their Dissolution in Water 13.3 Groundwater as a Closed System for Atmospheric Noble Gases 13.4 Studies on Atmospheric Noble Gas Retention in Groundwater Systems: Cold Groundwater 13.5 Further Checks on Atmospheric Noble Gas Retention: Warm Groundwater 13.6 Identication of the Nature of the Unsaturated Recharge Zone: A Porous Medium or a Karstic System 13.7 Depth of Circulation and Location of the Recharge Zone 13.8 Paleotemperatures 13.9 Sample Collection for Noble Gas Measurements 13.10 Summary Exercises

264 267 268 270 271 271 272 273 275 277 285 286 287 287 288 290 291 298


302 303 305 310 311


Helium-4 and Argon-40 Long Range Dating 312 14.1 Sources of Radiogenic 4He Dissolved in Groundwater 312 14.2 Parameters Determining Helium Concentration in Groundwater 313



14.3 14.4 14.5 14.6 14.7 14.8 14.9 14.10

14.11 14.12 14.13 14.14 15.

Case Studies and Observed Trends in the Distribution of Helium Concentrations in Groundwater Systems Mantle Helium The Helium-Based Groundwater Age Equation Comparison of Helium-Based Water Ages and Hydraulically Calculated Ages Does Helium Diffuse Through the Upper Crust? Helium Concentration Increases with Depth: Groundwater Acts as a Sink of Helium Effect of Mixing of Groundwaters of Different Ages on the Observed Helium Concentration Helium Loss or Gain Due to Phase Separation Underground or During Ascent to the Sampling Point: Modes of Identication and Correction Internal Checks for Helium Ages The Issue of Very Old Groundwaters Conclusions Summary Exercises

314 316 316 317 318 318 320

321 324 325 326 326 328 328 329 330 330 331 334 336 337 337

Paleoclimate, Paleohydrology, and Groundwater Dating Interrelations 15.1 Scope of the Problem 15.2 The Need to Reconstruct Paleo-Input Values 15.3 Stagnant Systems as Fossil Through-Flow Systems 15.4 Screening of Data for Samples of Last Minute Mixing of Groundwaters of Different Ages 15.5 Paleohydrological Changes 15.6 Paleoclimate Changes 15.7 Selecting Sites for Noble Gas Based Paleotemperature Studies 15.8 Stages of Data Processing 15.9 Summary Exercises Man and Water

Part IV. 16.

Detecting Pollution Sources 16.1 Scope of the Problem 16.2 Detection and Monitoring of Pollutants: Some Basic Rules 16.3 Groundwater Pollution Case Studies 16.4 Summary of Case Studies 16.5 Summary Exercises

340 340 341 343 376 377




Sustainable Development of GroundwaterUrban and Statewide Management 17.1 Sustainable Development 17.2 Man and Groundwater: A Historical Perspective 17.3 The Concern Over Groundwater Quality: A Lever for the Demand of Clean Nationwide Management 17.4 The Value of the Environment: An Essential Parameter in Economic Calculations 17.5 Recharge and Its Controls 17.6 Overpumping Policy: The Through-Flow Systems 17.7 Optimization of Pumping Rates in the Through-Flow System 17.8 Optimal Utilization of the Groundwater Resource 17.9 Groundwater Aspects of Urban and Statewide Development Planning and Management 17.10 Summary Exercises Water Quality Standards, Monitoring, Data Banks, and Education Activities 18.1 Drinking Water Standards 18.2 Water Monitoring Networks 18.3 Active and Efcient Data BanksThe Structure and the Challenges 18.4 Water-Related Education Activities 18.5 Summary Exercises Hydrochemists Reports 19.1 Why Reports? 19.2 Types of Reports 19.3 Internal Structure of Reports

378 378 378 379 380 381 382 384 385 386 391 392 392 394 401 403 409 411 411 411 412 420 438 451



Answers to Exercise Questions References Index


1.1 The Concealed Nature of Groundwater

Groundwater is a concealed uid that can be observed only at intermittent points at springs and in boreholes. Aquifers and ow paths are traditionally deduced by information retrieved from drilling operations, for example, rock cuttings and occasionally cores, but these are poor small-scale representatives of the large systems involved. This feature is familiar to geologists who try to predict the lithological and stratigraphic column to be passed by a new borehole. The outcome reveals time and again a higher spatial complexity and variability than predicted by interpolation of data available from existing boreholes. Prediction of hydraulic barriers, as well as prediction of preferred ow paths, based on knowledge of the regional geology are short-handed as well. Water properties have also been measured traditionally, but they were mostly limited to the depth of the water table, or the hydraulic head, temperature, and salinity. Modern chemical and isotope hydrology encompasses many more parameters and deals with the integrative interpretation of all available data. The concealed nature of groundwater gets gradually exposed.

1.2 Groundwater Composition

Water molecules are built of two elements: hydrogen (H) and oxygen (O). The general formula is H2O. Different varieties of atoms with different

Chapter 1

masses, called isotopes, are present in water, including light hydrogen, 1H (most common); heavy hydrogen, called deuterium, 2H or D (rare); light oxygen, 16O (common); 17O (very rare); and heavy oxygen, 18O (rare). Thus, several types of water molecules occur, the most important being H16O 2 light, the most common water moleculeand HD16O and H18Oheavy, 2 rare water molecules. The major terrestrial water reservoirs, the oceans, are well mixed and of rather uniform composition. Upon evaporation, an isotopic separation occurs because the light molecules are more readily evaporated. Thus water in clouds is isotopically light compared to ocean water. Upon condensation, heavier water molecules condense more readily, causing a reversed fractionation. The degree of isotopic fractionation depends on the ambient temperature and other factors which are discussed in Chapter 9. Water contains dissolved salts, dissociated into cations (positively charged ions) and anions (negatively charged ions). The most common dissolved cations are sodium (Na), calcium (Ca2 ), magnesium (Mg2 ), and potassium (K). The most common anions are chloride (Cl), bicarbonate (HCO ), and sulfate (SO2 ), discussed in section 5.5. The 3 4 composition of groundwater, that is, the concentration of the different ions, varies over a wide range of values. Water also contains dissolved gases. A major source is air, contributing nitrogen (N2), oxygen (O2), and noble gases (Chapter 13) helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe). Other gases, of biogenic origin, are added to the water in the ground, for example, carbon dioxide (CO2), methane (CH4), and hydrogen sulde (H2S). Biogenic processes may consume the dissolved oxygen. Cosmic rays interact with the upper atmosphere and produce a variety of radioactive isotopes, three of which are of special hydrological interest: (1) 3H, better known as tritium (T), the heaviest hydrogen isotope, (2) carbon-14 (14C), the heaviest isotope of carbon, and (3) chlorine-36 (36Cl), a rare isotope of chlorine. The rate of radioactive decay is expressed in terms of half-life, that is, the time required for atoms in a given reservoir to decay to half their initial number. The three radioactive isotopestritium, 14C, and 36Clare incorporated into groundwater. They decay in the saturated zone (section 2.2), providing three semiquantitative dating toolsfor periods of a few decades, to 25,000 years, and 105 to 106 years (respectively, sections 10.4, 11.4, and 12.2). The three isotopes also have been produced by nuclear bomb tests, complicating the picture but providing additional information. Rocks contain uranium and thorium in small concentrations, and their radioactive decay results in the production of radiogenic helium-4 (4He). The helium reaches the groundwater and is dissolved and stored. With time,


radiogenic helium is accumulated in groundwater, providing an independent semiquantitative dating method (section 13.9) useful for ages in the range of 104 to 108 years.

1.3 Information Encoded into Water During the Hydrological Cycle

The hydrological cycle is well known in its general outline: ocean water is evaporated, forming clouds that are blown into the continent, where they gradually condense and rain out. On hitting the ground, part of the rain is turned into runoff, owing back into the ocean, part is returned to the atmosphere by evapotranspiration, and the rest inltrates and joins groundwater reservoirs, ultimately returning to the ocean as well. Hydrochemical studies reveal an ever-growing amount of information that is encoded into water during this cycle. It is up to the hydrochemist to decipher this information and to translate it into terms usable by water management personal (Fig. 1.1). Rain-producing air masses are formed over different regions of the oceans, where different ambient temperatures prevail, resulting in different degrees of isotopic fractionation during evaporation and cloud formation. This explains observed variations in the isotopic composition of rains reaching a region from different directions or at different seasons. In terms of this chapter, we can say that water is encoded with isotopic information even in the rst stages of the water cyclecloud formation. Wind carries water droplets of seawater which dry and form salt grains. These windborne salts, or sea spray, reach the clouds and are carried along with them. Sea spray also reaches the continents as aerosols that settle on surfaces and are washed into the ground by rain. Rainwater dissolves atmospheric N2 and O2 and the rare gases as well as CO2. In addition, radioactive tritium, 14C, and 36Cl are incorporated into the hydrological cycle and reach groundwater. Manmade pollutants reach rainwater through the air. The best known is acid rain, which contains sulfur compounds. A large variety of other pollutants of urban life and industry are lifted into the atmosphere and washed down by rain. As clouds move inland or rise up mountains, their water condenses and gradually rains out. Isotopic fractionation increases the deuterium and 18O content of the condensed rain, depleting the concentration of these isotopes in the vapor remaining in the cloud. As the cloud moves on into the continent or up a mountain, the rain produced becomes progressively depleted in the heavy isotopes. Surveys have been developed into a source of information on distance of recharge from the

Chapter 1

Fig. 1.1 Information coded into water along its surface and underground path: right at the beginning, water in clouds is tagged by an enrichment of light hydrogen (1H) and oxygen (16O) isotopes, separated during evaporation. Cloud water equilibrates with the atmosphere, dissolving radioactive tritium (T) and radiocarbon (14C) produced naturally and introduced by nuclear bomb tests. Also, atmospheric gases are dissolved, the most important being oxygen (O2), nitrogen (N2), and the noble gases (He, Ne, Ar, Kr, and Xe). Gas dissolution is dependent on temperature and altitude (pressure). Sea spray reaches the clouds, along with urban and industrial pollutants. As clouds produce rain, heavy hydrogen (D) and heavy oxygen (18O) isotopes are preferentially enriched, leaving isotopically depleted water in the cloud. Thus inland and in mountainous regions rains of different isotopic compositions are formed. Upon hitting the ground, rainwater dissolves accumulated sea spray aerosols, dust particles, pesticides, and fertilizers. These are carried to rivers or introduced into the ground with inltrating water. Sewage and industrial wastes are introduced into the ground as well, mixing with groundwater. Underground, water is disconnected from new supplies of tritium and 14C, and the original amounts decay with time. On the other hand, radiogenic helium (4He) and argon (40Ar), produced in rocks, enter the water and accumulate with time. As water enters the soil zone it becomes enriched with soil CO2 produced by biogenic activity, turning the water into an acid that interacts with rocks and introducing dissolved ions into the water. The deeper water circulates, the warmer it gets due to the existing geothermal gradient.

coast and recharge altitude, parameters that help identify recharge areas (sections 9.7 and 9.8). Upon contact with the soil, rainwater dissolves accumulated sea spray and dust as well as fertilizers and pesticides. Fluid wastes are locally added, providing further tagging of water.


Inltrating water, passing the soil zone, becomes loaded with CO2 formed in biogenic processes. The water turns into a weak acid that dissolves soil components and rocks. The nature of these dissolution processes varies with soil and rock types, climate, and drainage conditions. Dissolution ceases when ionic saturation is reached, but exchange reactions may continue (section 6.8). Daily temperature uctuations are averaged out in most climates at a depth of 40 cm below the surface, and seasonal temperature variations are averaged out at a depth of 1015 m. At this depth the prevailing temperature is commonly close to the average annual value. Temperature of shallow groundwater equaling that of the rainy season indicates rapid recharge through conduits. In contrast, if the temperature of shallow groundwater equals the average annual temperature, this indicates retardation in the soil and aerated zone until temperature equilibration has been reached. Further along the ow path groundwater gets heated by the geothermal heat gradient, providing information on the depth of circulation or underground storage (sections 4.74.9). While water is stored underground, the radioactive isotopes of tritium, 14 C, and 36C decay and the concentrations left indicate the age of the water. At the same time, radiogenic 4He accumulates, providing another age indicator. A summary of the information encoded into water during its cycle is given in Fig. 1.1.

1.4 Questions Asked

Many stages of the water cycle are described by specic information implanted into surface water and groundwater. Yet, eld hydrochemists have limited access to the water, being able to measure and sample it only at single pointswells and springs. Their task is to reconstruct the complete water history. A list of pertinent topics is given below.

1.4.1 Water Quality

Because groundwaters differ from one place to another in the concentration of their dissolved salts and gases, it is obvious that they also differ in quality. Water of high quality (low salt content, good taste) should be saved for drinking, irrigation, and a number of specic industries. Poorer water (more salts, poor taste) may be used, in order of quality, for domestic purposes (other than drinking and cooking), certain types of agricultural applications, stock raising, and industrial consumption. The shorter water resources are, the more important become the management manipulations that make sure each drop of water is used in the best way.

Chapter 1

1.4.2 Water Quantity

As with any other commodity, for water the target is the more, the better. But, having constructed a well, will we always pump it as much as possible? Not at all. Commonly, a steady supply is required. Therefore, water will be pumped at a reasonable rate so the water table will not drop below the pump inlet and water will ow from the host rocks into the well at a steady rate. Young water is steadily replenished, and with the right pumping rate may be developed into a steady water supply installation. In contrast, pumping old water resembles miningthe amounts are limited. The limitation may be noticed soon or, as in the Great Artesian Basin of Australia, the shortage may be felt only after substantial abstraction, but in such cases the shortage causes severe problems due to local overdevelopment. Knowledge of the age of water is thus essential for groundwater management. The topic of water dating is discussed in Chapters 1013.

1.4.3 Hydraulic Interconnections

Does pumping in one well lower the output of an adjacent well? How can we predict? How can we test? Everyone knows that water ows down-gradient, but to what distances is this rule effective? And is the way always clear underground for water to ow in all down-gradient directions? The answers to these questions vary from case to case and therefore a direct tracing investigation is always desired but rarely feasible. Compositional, age, and temperature similarities may conrm hydraulic interconnections between adjacent springs and wells, whereas signicant differences may indicate ow discontinuities (sections 2.8, 4.4, and 6.5).

1.4.4 Mixing of Different Groundwater Types

Investigations reveal an increasing number of case studies in which different water types (e.g., of different composition, temperature, and/or age) intermix underground. The hydrochemist has to explore the situation in each study area. We are used to regarding groundwater as being of a single (homogeneous) type, which it often is. In such cases a quality analysis represents the whole water body, and similarly all other parameters measured reect the properties of the entire system. But when fresh recent groundwater is mixed with varying quantities of saline old groundwater, the hydrochemists life becomes tough and interesting. The rst task is to nd the properties of the end members of the intermixing waters and their origins (sections 6.6 and 6.7). Then it is possible to recommend proper exploitation policies, balancing the need for the better water type with the demand for large water quantities.


1.4.5 Depth of Circulation

Understanding a groundwater system includes knowledge of the depth of circulation. Temperature can supply this information: the temperature of rocks is observed to increase with depth and the same holds true for water kept in rock systemsthe deeper water is stored, the warmer is it when it issues from a spring or well (section 4.7).

1.4.6 Location of Recharge

Every bottle of water collected at a spring or well contains information on the recharge location. Water molecules are separated during precipitation from cloudsmolecules with heavier isotopes being rained out more efciently than molecules with lighter isotopes. As a result, clouds that are blown to high mountains precipitate light rain. Study of the isotopic composition of groundwaters provides clues to the recharge altitude (section 9.8) and, hence, provides constraints on the possible location of recharge.

1.4.7 Sources of Pollution

The major topics the hydrochemist has to deal with regarding pollution are . . Early detection of the arrival of pollutants into groundwater in order to provide warning in due time, allowing for protective action Identication of pollutant input sources

This brings us back to the problems of groundwater intermixing and hydraulic interconnections. It also brings to mind the urgent need for basic data to be collected on nondisturbed systems so that changes caused by contamination can be detected at an early stage.

1.5 Phenomenological Conceptual Models and Mathematical Models

The ultimate goal of a hydrochemical study is the construction of a conceptual model describing the water system in three spatial dimensions with its evolution in time. To achieve this goal a large number of observations and measurements are required to nd the site-specic setups. Thus, at the basic stage of investigation a phenomenological approach is required. The phenomenological conceptual model is mainly qualitative, recognizing recharge areas; topographic relief; terminal bases of drainage; modes of water uptake; lithological compositions; geological structures; the number and nature of aquifers and aquicludes; karstic features and other

Chapter 1

preferred ow paths; storage capacities; ow directions and approximate ow velocities; degrees of connement; identication of compartments of complete stagnation (entrapment); depths of groundwater ow and storage; response to rain, ood, and snowmelt events; water ages; and sources of pollution. A phenomenological conceptual model is best summarized in diagrams. The conceptual model is needed to plan further stages of investigation, to forecast system behavior, and to provide the necessary base for mathematical modeling. Phenomenological models are not only a scientic necessity, but are also useful in dealing with clients or nancing authorities. A preliminary conceptual model may provide a useful introduction to research proposals, clarifying the suggested working plan and budgetary needs. Finally, the conceptual model is a must for nal reports (section 19.3). A mathematical model is the outcome of a set of mathematical operations applied to sets of data and based on premises. The appeal of mathematical models is their quantitative aspect. However, mathematical models suffer from technical restrictions to accommodate the three spatial dimensions, ranges of measured parameters, changes of the groundwater regime with season, climatic uctuations, and response to human intervention. Thus, mathematical modeling necessitates simplications, for example, application of single hydraulic conductivity coefcients selected to represent entire study areas or large sections therein (section 2.7), assumption of lithological homogeneity, application of simplied relief and water table congurations so they may be described by simple mathematical equations and other boundary conditions. Assumptions are valid as long as they are backed by a phenomenological model that is based on real eld data. Otherwise, they are camouaged unknowns, bringing the mathematical calculations to a stage in which the number of unknowns is larger than the number of relevant equations. Hence the mathematical model should be based on a phenomenological model.

1.6 Economic Considerations of Field Hydrochemistry

Applied water research is nearly always conducted with a restricted budget. Traditionally the larger sums go to the construction of weirs and other discharge measuring devices in surface water studies and the drilling of new wells in groundwater studies. Little money is allocated to hydrochemical investigations. The ratio of outcome to cost is, however, in many cases in favor of hydrochemical studies.


New drillings are traditionally conducted to check water occurrences, to establish the depth of water tables, and to be equipped for pumping new niches of known aquifers. Inclusion of hydrochemical studies as an integral part of the drilling operation may double or triple the amount and quality of information gained, with only a small increase in costs. A number of examples are given below.

1.6.1 Measurements During Drilling, Providing Insight into the Vertical Distribution of Water Bodies
Blind drilling is common, aiming at a specic water horizon or aquifer. It is the hydrochemists task to convince the drilling organization that drilling should be stopped at intervals, water removed so that new water enters the well, and the following measurements carried out: . . . . Water level Temperature Electrical conductivity (indicating salinity) Samples collected for chemical and isotopic analyses

This will provide vital information on the vertical distribution of water horizons and their properties (section 7.2). Admittedly, arresting a drilling operation costs money, but the gained information is indispensable because water layers may otherwise be missed. Savings may be made by conducting hydrochemical measurements and sampling at planned breaks in the drilling operation on weekends and holidays or during unplanned breaks due to mechanical troubles.

1.6.2 Initial and Current Databases

Whenever a new well is completed, the abstracted aquifer should be studied in detail, including water table and temperature measurements and complete laboratory analysis of dissolved ions and gases, stable isotopes, and age indicators such as tritium, 14C, and 36Cl. Analysis for suspected pollutants, for example, fertilizers, pesticides, pollutants from local industries, and domestic sewage, should be carried out as well. This wealth of data is needed to provide answers to the questions raised in section 1.4. Pumping changes the underground pressure regime, and uids begin to move in new directions. Thus information that was not collected at the very beginning of a well operation is lost and may not be obtained later. The hydrologic evolution of ow patterns induced by human activity in exploited water systems can be established by frequent comparisons to the initial situation (section 7.5).


Chapter 1

As can be sensed, hydrochemical investigations produce an enormous number of observations and measured results. This is the strength of this discipline, but the ood of data has to be well registered in active and userfriendly databanks. Much thinking and care should be devoted to the administration of databanks to ensure they do not turn into data sinks (section 18.3).

1.6.3 Periodically Repeated Hydrochemical Measurements (Time Series)

There are questions that cannot be answered by the mere placement of new wells. Information is needed on the Number of water types that are intermixed underground Seasonal variations in water quality and quantity Inuence of pumping operations in adjacent wells This information may be obtained by conducting periodically repeated measurements in selected wells and springs (section 18.2). The costs of repeated measurements are small in comparison to drilling, and they provide information not otherwise available, signicantly increasing the understanding of the water system in terms needed for its management. The economical value of hydrochemical studies also has wider aspects, as they may reduce the number of new drillings needed or improve their location. The price of hydrochemical measurements is small compared to drilling expenses, but they should be minimized by careful planning and proper selection of the parameters measured at each stage of the study and proper selection of water sampling frequencies. These topics are discussed in section 18.2.

1.7 Environmental Issues

Intervention of man in groundwater regimes is intensive in densely populated areas, and quality deterioration is manifold; examples being . . . Encroachment of saline groundwater as a result of local lowering of water tables in unconned systems, and reduction of water pressures in conned and stagnant systems (section 17.6) Encroachment of seawater in coastal wells as a result of overpumping and an extreme lowering of the water table (section 17.6) Reduction of local recharge due to urbanization-related sealing of the ground and formation of street runoff (section 17.9.2)



Pollution as a result of irrigation, industry, sewage, fuel spillage, etc.

The common thread in these water deterioration processes is their being cases of intermixing of natural waters of different qualities or mixing of uncontaminated water with contaminated efuents. Hence the need (1) to be familiar with the methodology of mixing identication and reconstruction of the properties of the involved end members (section 6.7) and (2) the establishment of initial databases (section 18.3).

1.8 Summary Exercises

Exercise 1.1: All the rivers ow into the sea . . . is written in Ecclesiastes. This remarkable observation was made more than 2000 years ago. What is remarkable about it? Which basic concepts of hydrology is it describing? Exercise 1.2: . . . and the sea does not ll up continues Ecclesiastes. The ancient observer raises a fundamental research problemhe draws attention to what seems to be a violation of a universal law, which he must have known. Which law is it? Exercise 1.3: The above citations make it clear that the concept of the water cycle was not known to the ancient philosophers. Which segments of the water cycle were concealed from the ancient scientists? Exercise 1.4: The introductory chapter is devoted to the encoding of information into water along the hydrological cycle. At which point is all this information erased? Exercise 1.5: What kinds of information are inscribed into water underground? Exercise 1.6: Comparing the landscape of the Moon and that of Earth, we realize the great impact of water in the latter case. What is it? Exercise 1.7: Which observation tells us that the oceans existed in the geological past?

Part I

~~~~~~~~ Observations and Measurements ; Conclusions ;; Working Hypotheses ;;; Criteria to Check the Hypotheses ~~~~~~~~


2.1 The Aerated Intake Zone

A typical well passes through two zones: an upper zone, usually of soilcovered rock, that contains air and water in pores and ssures and a lower zone, often of rock, that contains only water in pores and ssures. This separation into two parts is observed everywhere, and the two zones have been named the aerated (air-containing) zone and the saturated (watersaturated) zone. The top of the saturated zone (where water is hit in a well) is called the water table (Fig. 2.1). The water table is described either in terms of its depth from the surface or as the altitude above sea level (section 2.2). The aerated zone is also called the vadose zone (from Latin vadosus, shallow). Its thickness varies from zero (swamps) to several hundred meters (in regions of elevated and rugged topography and in arid climates), but it is commonly 525 m. In most cases the aerated zone has two parts: soil at the top and a rocky section beneath. The soil, formed by weathering and biogenic processes, varies in thickness from zero (bare rock surface) to a few meters, reaching maximal thickness in alluvial valleys. The soil zone is characterized by the plants that grow in it, their roots penetrating 1040 cm, but certain plants, mainly trees, have roots that grow as deep as 2030 m. Roots may penetrate the lower rocky part of the aerated zone, occasionally reaching the water table. Plants respire and liberate CO2 into the soil pores. Bacteria decompose plant remains in the soil, adding to the CO2 of the soil air. This biogenic CO2 dissolves in inltrating water, producing carbonic acid, that slowly but


Chapter 2

Fig. 2.1 A schematic section through typical wells: at the upper part the soil and rocks contain air and water in pores and ssures, forming the aerated zone. Below occur rocks with only water in their pores and ssures, forming the saturated zone. The top of the saturated zone is the water table, recognizable in wells as the depth at which water is encountered.

continually dissolves minerals and rock components. This process creates soil and provides recharging water with dissolved salts (section 6.8). Intake of water in the aerated zone is either by inltration into the soil cover or, on bare rock surfaces, by inltration into intergranular pores (as in sand-stone), ssures and joints (as in igneous rocks or quartzite), or dissolution conduits and cavities (limestone, dolomite, gypsum, rock salt). Only pores and ssures that are interconnected, or communicate, are effective to inltration. Water inltration in a sandy soil may be described as water movement in a homogeneous granular medium (or as in a sponge). Water descends in this setting in downward-moving fronts, or in a piston-like ow (Fig. 2.2). In such a mode of ow a layering exists, the deeper water layers being older than the shallower ones. Measurements of tritium and other contaminants

Fig. 2.2 Piston ow of water inltrating into a homogeneous granular soil (spongetype ow). A layered structure is formed, lower water layers being older than shallow ones. Penetration velocities are observed to range from a few centimeters to a few meters per year.

Basic Hydrological Concepts


reveal that such piston ows proceed at velocities of a few centimeters to a few meters a year. This velocity depends on the porosity of the soil, the degree of pore interconnection, the amount and mode of distribution of local precipitation, and drainage conditions. In contrast to the sponge-type ow, recharge into the ground is often rapid, through conduits and zones of preferred transmissivity. Examples of such conduits are open desiccation cracks, old desiccation cracks that have been lled up with coarse material, living and decayed roots, animal holes or bioturbations, and gravel-packed channels of buried streambeds (Fig. 2.3). Karstic terrains (section 2.9) provide extreme examples of recharge via conduits. In most cases water descends through the aerated zone in a combined mode, that is, through intergranular pores and through conduits that cross the granular medium (Fig. 2.4).

2.2 The Saturated Zone and the Water Table

Inltrating water settles by gravity, reaching a depth at which all voids in the ground are lled with water. This portion of the ground is called the saturated zone. The water in this zone forms a continuous medium interwoven with the solid matter system. The water in the saturated zone settles with a smooth horizontal upper face, called the water face, or water table. By analogy, water poured into a vessel settles with a smooth horizontal upper facea miniature water table. The depth of the water table, or the water level, is expressed either in relation to the land surface or as the altitude above sea level. The depth of the water table varies from zero, in marshy areas, to several hundred meters, in dry mountainous terrains. A depth of a few tens of meters is common. Measurements of the water table are of prime interest for management purposes and for the establishment of ow directions. Study of water table

Fig. 2.3 Enhanced recharge through parts of high conductance in soil, alluvium, and nonconsolidated rocks: (1) gravel in buried streambeds; (2) open desiccation cracks; (3) old desiccation cracks lled with coarse material; (4) animal holes; (5) plant roots.


Chapter 2

Fig. 2.4 Inltration of recharge water in a combined mode: part of the water moves slowly through the granular (mainly soil) portion of the aerated zone and part moves fast through open conduits in zones of high transmission.

uctuations is most valuable: rapid response to rain, ood events, or snowmelt indicates fast recharge via conduits. Delayed response indicates slow inltration through a porous medium. Changes in the water table, caused by pumping in adjacent wells, establishes the existence of hydraulic interconnections between the respective wells (sections 4.1 and 4.2). The slope of the water table is dened by three major factors: the base of the drainage system (sea, lake, river), the topography of the land surface, and the occurrence of impermeable rock beds. The saturated zone usually contains strata of varying permeabilities, forming aquifers and aquicludes, described in the following sections.

2.3 Aquifers and Aquicludes 2.3.1 Aquifers

Rock beds at the saturated zone that host owing groundwater are called aquifers (from Latin aqua, water; ferre, to bear or carry). Aquifer rocks contain the water in voidspores and ssures. The size and number of voids and the degree of interconnection between those pores and ssures dene the qualities of the aquifers. The same properties dene inltration efciency and capacity of intake of recharge water. These properties are discussed below for different rocks. Conglomerates. These rock deposits are made up of rock pebbles cemented to different degrees. If poorly cemented, conglomerates are extremely efcient water intake systems; they form aquifers with large storage volumes, and water ows relatively fast through them (provided gradients are steep enough and drainage conditions are good). Often conglomerates are cemented by calcite, iron oxides, or silica. Cementation reduces the water-carrying capacity of an aquifer, and in extreme cases conglomerates are so tightly cemented that they act as aquicludes.

Basic Hydrological Concepts


Sandstone. Sandstone is in most cases composed of quartz grains with pores constituting 1050% of the rock volume. The pores are interconnected, providing high inltration efciencies and providing sandstone aquifers with high storage capacities and rapid water throughow. Cementation reduces the pore space, but cemented sandstone tends to develop mechanically formed ssures that let water through. Limestone and dolomite. These carbonate rocks are often well crystallized and can be poor in interconnected pores. However, limestone and dolomite tend to fracture under tectonic stress, and through such fractures groundwater can move. Water can have two completely different effects on the fractures: either the water lls up the ssures by precipitation of carbonates or, under high ow conditions, the water dissolves the rock and causes further opening. Dissolution of limestone and dolomite may thus create surface and subsurface conduits that enhance intake of recharge water and form high-conducting aquifers with large water storage capacities. Karstic systems are the result of extreme dissolution activity in hard carbonate rocks (section 2.9). Igneous rocks. Granite and other intrusive igneous rocks have intrinsically well-crystallized structures with no empty pores. However, being rigid they tend to fracture and may have a limited degree of inltration capacity and aquifer conductivity. Weathering in humid climates may result in extensive formation of soil, but little dissolution opening of fractures. Thus, granitic rocks may form very poor to medium quality aquifers. Basalt and other extrusive lava rocks are similar to granitic rocks in having no pores and tending to fracture. In addition, lava rocks often occur in bedded structures, alternating with paleosoils and other types of conducting materials, for example, rough lava ow surfaces. Thus, basaltic terrains may have medium lateral ow conductivities. Weathering of basaltic rocks and paleosoils produces clay minerals that tend to clog fractures. Tuff (a rock formed by fragmental volcanic ejecta) is porous when formed, but is readily weathered into clay-rich impervious soils. Metamorphic rocks. Quartzite, schist, gneiss, and other metamorphic rocks and metasediments vary in their hydrological properties, but in most cases are fractured and transmit water. In rainy zones weathering may produce clays that occasionally clog the fractures. The rocks discussed in this section have intrinsically medium to good inltration efciency, aquifer conductance, and storage capacities. These features may be developed to different degrees as a result of secondary


Chapter 2

processes such as tectonic fracturing and chemical dissolution opening on the one hand and clogging by sedimentation and weathering products on the other hand. Thus, close study of rock types and of accompanying features are essential parts of hydrological investigations.

2.3.2 Aquicludes
Rock strata that prevent passage of groundwater are called aquicludes (from Latin aqua, water; claudere, to close). Aquicludes are important components of groundwater systems because they seal the aquifers and prevent water from inltrating to great depths. Aquicludes are essential to the formation of springs and shallow accessible aquifers. Aquiclude rocks have low water conductivity caused by a lack of interconnected voids or conduits. A number of common aquiclude-forming rocks are discussed below.

Clay. Clay minerals have several characteristics that make them good aquicludes: . . . When consolidated, they have effectively no interconnected pores. They swell, closing desiccation fractures or tectonic fractures. They are plasticanother property that makes clays effective sealing agents.

The effectiveness of clay aquicludes depends on the type of clay, montmorillonite being perhaps the best. The thickness of the clay aquiclude is of prime importancea clay bed 1 m thick may be a signicant barrier to underground water movement, but water may slowly leak through. The thicker the aquiclude, the higher is its sealing efciency. Clay aquicludes with a thickness of several hundred meters are known.

Shales. Shales are derivatives of clays, formed in slow diagenetic processes. Shales have little or negligible swelling capacity and have medium plasticity. They form effective aquicludes at thicknesses of at least a few meters to tens of meters.

Igneous rocks. Large igneous bodies, such as stocks or thick sills, often act as aquicludes because they lack interconnected fractures or dissolution conduits. Dikes and sills may act as aquicludes if they are either very fresh and not fractured or are weathered into clay-rich rocks.

Basic Hydrological Concepts


2.4 Recharge
The term recharge relates to the water added to the groundwater system, that is, to the saturated zone. Thus, recharge is the balance between the amount of water that inltrates into the ground and evapotranspiration losses. The location of recharge areas is of prime importance in modern hydrochemistry, as such areas have to be protected in order to preserve groundwater quality. Urbanization, agriculture, and almost any other kind of human activity may spoil the quality of recharge water. Limitations on the use of fertilizers and pesticides in recharge areas are often enforced, along with limitations on mining and other earth-moving activities. Since these limitations have nancial impacts, an increasing number of cases are being taken to court, and hydrochemists may be asked to deliver expert opinions involving the identication of areas of active recharge. The following are a few features characterizing recharge regions: . . . . . . . Depth of water table is at least a few meters below the surface. Water table contours show a local high. Signicant seasonal water table variations are noticed. Local groundwater temperatures are equal to, or several degrees colder than, the average ambient annual temperature. Effective water ages are very recent (a few months to a few years). Salt content is low in most cases in nonpolluted areas (less than about 800 mg/l total dissolved ions). Surface is covered by sand, permeable soil, or outcrops of permeable rocks.

2.5 Discharge
The term discharge relates to the emergence of groundwater at the surface as springs, water feeding swamps and lakes, and water pumped from wells. Discharge is the output of groundwater. The rate of discharge is measured in units of volume per time, for example, cubic meters per hour (m3/h) (section 4.10). The bulk of the groundwater is drained into terminal bases of drainage, which in general are the seas. Most of this drainage is concealed, but can be detected indirectly, for example, by the presence of fresh water in shallow wells at the seashore or in offshore boreholes. Discharge areas away from the terminal base of drainage warrant identication in relation to drainage operations, water exploration, and water quality preservation. Several features characterize discharge areas:


Chapter 2

. . .

Water table levels mark, in most cases, a high in the water table contour map. Water temperatures are a few degrees above the average annual ambient temperature, reecting warming by the thermal gradient while circulating at depth (section 4.8). Waters are either fresh or saline (if they have passed through salinizing rocks) (section 3.1).

2.6 Evapotranspiration
Only part of the water inltrating into the ground keeps moving downward into the saturated groundwater zone. An important part of inltrated water is transferred back into the atmosphere. Two major mechanisms are involved: evaporation and transpiration, together called evapotranspiration. Evaporation is a physical process, caused by heat energy input, providing water molecules with kinetic energy that transfers them from an interpore liquid phase into a vapor phase. Evaporation depends on local temperature, humidity, wind, and other atmospheric parameters as well as soil properties. A maximal value is provided by the extent of evaporation from an open water body; this varies from place to place in the range of 1 2 m/year. Taken at face value, this would imply that no effective recharge occurs in areas that have an average annual precipitation rate lower than the potential evaporation rate measured in an open water body. This is not the case, however, as effective recharge is known in regions that have as little as 70 mm average annual rainfall. This indicates that water inltrated into the ground is partially protected from evaporation. In fact, evaporation occurs mainly from the uppermost soil surface, and when this is dry further evaporation depends on capillary ascent of water, which is a slow and only partially efcient process. It seems that water that has inltrated to a depth of 3 m is safe from capillary ascent and evaporation. From this discussion it becomes clear that the relative contribution of precipitation to recharge is proportional to the amount of rain falling in each rain event. Intensive rain events push water deep into the ground, contributing to recharge, whereas sporadic rains only wet the soil, and the water is then lost by subsequent evaporation. The mode of rainfall and degree of evaporation inuence groundwater composition. High degrees of evaporation result in enrichment of the heavier stable isotopes of hydrogen and oxygen (sections 9.3 and 9.6) and in higher concentrations of dissolved salts. Transpiration is the process by which plants lose water, mainly from the surfaces of leaves. Plants act as pumps, their roots extracting water from the soil and the leaves transpiring it into the atmosphere. Thus the depth of

Basic Hydrological Concepts


the transpiration effect on soil moisture is dened by the depth of a plants root system. The latter is most intensive to 40 cm and drops to almost nil at depths greater than 2 m. Roots of certain plants, mainly trees, are occasionally observed to penetrate to 2030 m.

2.7 Permeability, Impermeability, and the Selection of Representative Values 2.7.1 Permeability Denition
A large sector of hydrology deals with through-ow systems, that is, groundwater systems that are recharged. A term is needed that expresses the ability of different rock types to let water inltrate and ow through. This term is the permeability coefcient, k. Henry Darcy, a French engineer, conducted experiments in 1856 in which he measured the ow velocity of water through a sand-lled tube. He found that the ow velocity (V) is directly proportional to the difference in hydraulic head (Dh), and is inversely proportional to the ow distance (Dl): V kDh=Dl where Dh/Dl is the hydraulic gradient. The coefcient of proportionality, k, depends on the rock properties and is case specic. Hence, k is called the coefcient of permeability. A convenient way to dene the coefcient of permeability, in order to compare its value for different types of rocks, is to determine its empirical value for hydraulic gradients of 458, that is, for Dh/Dl 1. In such cases k V. The permeability coefcient (k) has the units of velocity, that is, distance/time. It is determined either in laboratory experiments or derived from pumping tests. Both methods are semiquantitative, but are still highly informative, as the values observed for common rocks span more than seven orders of magnitude. A variety of units are in usem/day being a common one. The following are a few of the average permeability or hydraulic conductivity values oating around in the literature, expressed in m/day: Shale, 107; clay, 106; sandstone, 102; limestone, 1; sand, 10; and gravel, 102

2.7.2 ImpermeabilityDiscussion of the Concept

Metal, glass, or ceramic vessels are generally agreed to be impermeable. Yet when it comes to rocks many hydrologists believe that there exist no impermeable natural materials, and all rocks are permeable, although to


Chapter 2

different degrees. This approach may be examined in light of the following analysis. The accepted permeability values, listed above, assign seven orders of magnitude difference between the permeability of clay or shale and that of sandstone or fractured limestone. Thus the resistance to ow exerted by 1 m of clay or shale is equivalent to the resistance exerted by 10,000 km of sandstone or fractured limestone (check the calculation!). Or, in a different example: if water ows a certain distance through limestone or sandstone in 1 year, it will take the water 10 million years (!) to ow an equivalent distance through clay or shale. These examples surely grant clay and shale the title of impermeability. The question of whether certain rocks are impermeable or possess a very low permeability is not just a matter of semantics; it is of principle importance to the understanding of hydrological systems as discussed in the following sections. A permeability of 107 m/day cannot be directly measured. It is assigned to clay by interpolation of indirect measurements, and this is done with prejudicebelieving a priori that clay is permeable. In this regard one may follow the physiciststhey do apply absolute terms, such as opaque, rigid, or impermeable. Why should not hydrologists do the same in the appropriate cases? Finally, there are examples of impermeable rock materials: . . Fluid inclusions are common in mineral crystals that are 107108 years old. The millimeter-thick walls of these crystals demonstrate the existence of impermeable rock materials. Oil and gas deposits are trapped for long periods, stored in permeable rocks that are engulfed by impermeable rocks (no one will claim that these are through-ow systems with active oil or gas recharge).

Along the same lines, groundwater is expected to exist in traps as well, engulfed by impermeable rocks. Related arguments and ample observations are discussed in sections 2.12 and 2.14.

2.7.3 Selection of Representative Permeability Coefcients

Permeability is observed to vary enormously in what looks like homogeneous rock bodies, and it varies much more between the different rock types that constitute a studied system. Disregarding this large range of different prevailing permeabilities, mathematical models accommodate only single permeability values for entire case studies or for large sections of studied systems. Thus representative values are selected in the frame of a whole list of model simplications. Such simplications can lead to

Basic Hydrological Concepts


misinterpretations and therefore should be avoided. If, however, it is decided to select a representative permeability coefcient for a model, the selection should at least be done correctly. The procedure adopted to select the representative permeability coefcient is rarely explained in published case studies. It seems that a common approach is to apply a weighted representative value. Let us examine this procedure in light of an example of a system that is composed of 90% fractured limestone (a coefcient of 1 m/day according to the accepted tables) and 10% of shale (107 m/day). The average weighted k will be k 0:961 0:16107 0:9 m=day The calculated value of 0.9 m/day is practically equal to the value of the high-conducting limestone and does not express at all the presence of the ow-resisting shale. Such a selected value is totally wrong and will lead to the calculation of an erroneously high ow velocity, a too short travel time, and a meaningless young water age (section 2.10). In order to properly represent the ow resistance of the shale, a harmonic mean seems much more plausible. In our example, k representative 90 10 : 90=10 10=107 1:06104 m=day This representative k reects the ability of even thin beds of clay and shale to stop through-ow. The discussed example provides a glimpse into the pitfalls that await the hydrologist in the selection of a representative permeability valuethe different modes of calculation can vary over almost ve orders of magnitude! It seems that a large list of modeled case studies should be revised in light of the necessity to properly select the applied k values. In most cases the application of the harmonic mean calculation provides signicantly lower k values, resulting in signicantly higher water ages (section 2.10), which is in good agreement with observed isotopic water ages (Chapters 11, 12, and 14) and in better agreement with structural geology observations.

2.7.4 Porosity
Water is stored in rocks mainly in pores. The effective porosity of a rock is the volume percentage of the rock that may contain water in pores. The values (Table 2.1) are high for nonconsolidated granular rockssoils, clays, silts, and gravels. The porosity is low for crystallized rocks such as limestone, dolomite, and most igneous rocks. Movement of water through

24 Table 2.1 Rock Porosities, Volume Percent Soils Clay Silt Coarse sand 5060% 4055% 4050% 3540% Fine sand Pebbles Sandstone Limestone 3035% 3040% 1020% 120%

Chapter 2

rocks is through interconnected pores, ssures, and conduits. Permeability is a measure of the ease of ow through rocks (hydraulic conductivity is another term). Permeability relates to the pores and voids that are interconnected; it differs from porosity, which is the total pore volume. Clay has a high content of water stored in the molecular lattice, but these water sites have practically no interconnections. Thus in spite of its high capacity for containing water, clay has a low permeability, making it a most efcient aquiclude. In contrast, sandstone (non-consolidated) has a high permeability, providing excellent aquifer properties.

2.8 Through-Flow Systems: Unconned and Conned 2.8.1 Phreatic (Unconned, Free Surface) Aquifers
Phreatic aquifers have free communication with the aerated zone. The synonym free surface aquifer relates to the free communication between the aquifer and the vadose zone. An example is shown in Fig. 2.5. The term phreatic originates from the Greek word for a well. Phreatic aquifers are the most exploited type of aquifer and most of the hydrochemists work is performed on them. Phreatic aquifers are the collectors of inltrating recharge water, and this process is well reected in

Fig. 2.5 Basic components of a phreatic groundwater system: intake outcrops, an aerated zone, the water table, the saturated zone that constitutes a water-bearing aquifer, and impermeable rock beds of the aquiclude that seal the aquifer at its base.

Basic Hydrological Concepts


the chemical, physical, and isotopic parameters of the aquifers water. Water table uctuations indicate the nature of recharge intake (sections 4.1 and 4.2), water table gradients indicate ow directions (section 4.3), water temperature indicates the nature of inltration and depth of circulation (section 4.7), and tritium and radiocarbon concentrations reect water ages and modes and velocity of ow (sections 10.7 and 11.8).

2.8.2 Conned Aquifers and Artesian Flow

Conned aquifers are water-bearing strata that are sealed at the top and the bottom by aquiclude rocks of low permeability (Fig. 2.6). Conned aquifers are commonly formed in folded terrains (section 3.4) and have a phreatic section, where the aquifer rock beds are exposed to recharge inltration, and a conned section, where the aquifer rock beds are isolated from the landscape surface by an aquiclude (Fig. 2.6). The water in the saturated zone of the phreatic section of a conned system exerts a hydrostatic pressure that causes water to ascend in wells. In fact, a conned aquifer can often be identied by the observation that water ascends in a borehole to a level higher than the level at which the water was rst struck. In extreme cases the water ascends to the surface, constituting an artesian well. This phenomenon of water ascending in a well and owing by itself was rst described in 1750 in the area of Artois, a province in

Fig. 2.6 Components of a conned aquifer with through-ow: tilted, or folded, water-bearing rock strata, sealed at the top and the base by aquicludes. Each active conned system also has a phreatic section at outcrops of the aquifer rocks. The level of the water table in the phreatic section denes the piezometric head in the conned section. Water ascends in boreholes drilled into conned aquifers. Water reaches the surface in artesian ow in boreholes that are drilled at altitudes lower than the piezometric head.


Chapter 2

northern France. The term artesian is applied to self-owing wells and to aquifers supporting such wells. The term semiartesian describes wells in which water ascends above the depth at which the water was struck but does not reach the surface. The level water reaches in an artesian well reects its pressure, called the piezometric, or conned, water head (Fig 2.6). In boreholes drilled at altitudes that are lower than the piezometric head, water will reach the surface in a jet (or wellhead pressure) with a pressure that is proportional to the difference between the altitude of the wellhead and the piezometric head. The piezometric head is slightly lower than the water level in the relevant phreatic section of the system due to the ow resistance of the aquifer. Conned aquifers often underlay a phreatic aquifer, as shown in Fig. 2.7. The nature of such groundwater systems may be revealed by data measured in boreholes and wells. The water levels in wells 1 and 2 of Fig. 2.7 did not rise after the water was encountered, and both wells reached a phreatic aquifer. Well 3 is artesian, and the drillers account should include the depth in which the water was struck and the depth and nature of the aquiclude. The hydraulic interconnection between well 1 and well 3 may be established by . . . Checking their water heads The resemblance of the relevant aquifer rocks Agreement of the measured dips at the outcrop and the depth at which the water was encountered at well 3

Fig. 2.7 A conned aquifer underlying a phreatic aquifer. The nature of such a system may be established by parameters measured at boreholes and wells (see text).

Basic Hydrological Concepts


Flow of groundwater in conned aquifers is determined by the water head gradient and by the degree to which the system is drained. In extreme cases water may be trapped in conned aquifers. The topic of water movement in conned aquifers is best studied by means of chemical and isotopic parameters (section 6.5).

2.8.3 Stagnant Aquifers (Groundwater Traps)

The discussion so far has dealt with through-ow systems that have active recharge and discharge. However, there are stagnant aquifers in which static groundwater is stored. This topic is discussed in section 2.12.

2.9 Karstic Systems: Paths of Preferred Flow

Hard calcareous rocks, that is, limestone and dolomite, develop specic features noticeable on the land surface: dissolution ssures, cavities, caves, and sinkholes in which runoff water disappears. On the slopes of such terrains occur springs with high discharges that often undergo a marked seasonal cycle. In such terrains intake of recharge water and underground ow are in open conduits (sections 2.1 and 2.2). A classical area of such conduit-controlled water systems has been described in the Karst Mountains of Yugoslavia, and from there originated the term karstic, pertaining to groundwater ow in dissolution conduits. Some basic features of karstic systems are depicted in Fig. 2.8. Sinkholes are inlets to conduits in which

Fig. 2.8 Components of a karstic system: sinkholes and ssures acting as inlets for rapid intake of runoff water; dissolution channels; water discharging in springs at local bases of drainage, for example, river beds; caves exposed at former dissolution channels formed at former (higher) drainage bases.


Chapter 2

runoff water can move rapidly into deeper parts of the system. Karstic springs occur at the base of local drainage basins, commonly major river beds or the seashore. Abandoned spring outlets remain hanging above new drainage bases, forming caves that can sometimes be rather deep. Dissolution conduits are formed by the chemical interaction of CO2 charged water with calcareous rocks (section 6.8). Karstic systems are often formed in generations. For example, during the Pleistocene, when the oceans had a lower water level, low-level karstic systems were formed in coastal areas. With the rise of sea level, higher karstic systems evolved. The karstic nature of recharge intake zones is often recognizable from specic geomorphic features, but this is not always the case. Karstic systems are occasionally concealed, and karstic outlets may occur tens of kilometers from the intake areas. Furthermore, paleokarstic conduits may be in operation in regions that at present have a semiarid climate. Thus indicators for karstic ow are needed. In small-scale studies, direct tracing of karstic underground interconnections has been successfully carried out with dyes, spores, and radioactive tracers. The limitations are The dependence on sinkholes as tracer inlets The logistics of tracing experiments that limits them to distances from hundreds of meters to at most a few kilometers Hydrological and hydrochemical indicators for karstic ow include . . . . . Rapid ow, revealed by very young groundwater ages (months to a few years) Water temperatures that maintain the intake temperatures (e.g., snowmelt temperatures) Signicant seasonal discharge uctuations Light stable isotope components, reecting composition of highaltitude precipitation and indicating lack of evaporation Chemical composition reecting contact with limestone and/or dolomite (section 6.8)

2.10 Flow Velocity and Groundwater Age

The term ow velocity sounds simple: the distance the water moves in a unit of time. In this sense it is also handled by Darcys experiment: V kDh=Dl In the experiment the water ows in a tube in which the water enters in one end, ows along the tube, and leaves at the other end. The impermeable

Basic Hydrological Concepts


walls of the tube turn it into a well-dened one-dimensional system, in which the point of recharge, the ow path, and the point of discharge are rigidly dened. The term groundwater age sounds simple as well: the time that has passed since a water parcel was recharged into the saturated water system. Or, in terms of travel time, the time that has passed since the water entered the ground until it reaches the point at which it is observed, for example, at a spring or a well. In a simplistic way one could compute the age of water (t) in Darcys experiment by dividing the length of the ow path (Dl) by the measured ow velocity (V): t Dl=V Again, we have to remember that the above equation holds true for the onedimensional setup of ow through a vertical tube. Most hydrology textbooks apply a tilted-tube version of the Darcy experiment in order to relate it to aquifers (Fig. 2.9). The analogy is possibly relevant only to tilted conned through-ow systems of the kind drawn in Fig. 2.7. However, such setups are scarce, since tilted rock systems rarely have adequate recharge intake areas, they do not serve as conduits, as they are often blocked by tectonically squeezed plastic rocks, and as a result of compaction their lower end is often buried beneath the base of drainage (Fig. 2.10). Thus, many conned systems host stagnant (trapped) groundwater (section 2.11), for which the Darcian equations are not geared (Mazor and Native, 1992, 1994; Mazor, 1995; Mazor et al., 1995; Fridman et al., 1995). The bulk of groundwater through-ow takes place in unconned systems. Precipitation falls over the entire surface of such systems and recharge is fed into them at every point. As a result, there is a constant

Fig. 2.9 Darcys law applied to a groundwater system: the velocity (V) at which water ows in the aquifer rocks is proportional to the coefcient of permeability (k) and the gradient (Dh/Dl). This is a greatly simplied approach, and a number of assumptions have to be checked with hydrochemical methods (see text).


Chapter 2

Fig. 2.10 Rock beds in a subsidence basin. The part above the terminal base of drainage, for example, the sea, functions as a through-ow system (arrows). The deeper rock beds are fossil through-ow systems that host stagnant groundwater as they are (1) covered by impermeable rocks, (2) bisected by plastic impermeable rocks that have been squeezed into stretch joints in the competent rock beds and in between bedding plane thrusts, and (3) placed in a zone of zero hydraulic potential.

increase in the water ux along the ow path. The base ow of the system accumulates water along its course, and as a result the ow velocity must increase as well. Hence no singular ow velocity exists in an unconned system. Similarly, water has no singular age in unconned systems. Water recharged at the upper reaches of a system has a long ow path and would attain a relatively high age along the ow path, but it is constantly mixed with more recent water that is recharged along the downow course. Thus unconned systems are characterized by constant mixing of waters of different ages. Hence there is no room for hydraulic (Darcian) calculation as it is built only for singular water age values. This brief discussion of the ow regime of an unconned system emphasizes its three-dimensional nature and the large variety of water uxes, velocities, and ages that prevail in each case study. The unconned groundwater regime differs fundamentally from the one-dimensional tube of Darcys experiment, with its particular properties (section 14.6). A completely different approach to the question of groundwater age is taken in the isotopic groundwater dating methods, using tritium, 14C, 36Cl, and 4H (sections 10.4, 11.4, 12.2, and 14.5). The short-range isotopic dating

Basic Hydrological Concepts


methods are informative for through-ow systems, and the long-range isotopic dating methods are especially useful for stagnant groundwaters.

2.11 Flow of Water: Basic Observations

The direction of ow of water is controlled by two major factors: . . Earths gravitational eld The degrees of hydraulic freedom

Four basic modes of water ow are observable in daily life (Fig. 2.11): Free fall, as in water that is released from a tilted bottle or as in rain. All directions are hydraulically free (three-dimensional degrees of hydraulic freedom), and the water is free to ow vertically under the force of gravity (Fig. 2.11a). Lateral overow, as in water reaching a lled tub. The water that lls the tub blocks the downow direction of the added water (two-dimensional degrees of hydraulic freedom), and the latter overows, that is, it ows laterally toward the bases of drainage (Fig. 2.11b). The observation that the water ows laterally indicates its surface (water table) is slightly tilted by the critical angle of ow. The latter is dened by the water viscosity. The water present in the deeper part of the tub does not owit is stagnant, bounded in a dead volume situated under

Fig. 2.11 Four basic modes of ow of water: (a) free fall, three-dimensional degrees of hydraulic freedom; (b) lateral overow, two-dimensional degrees of hydraulic freedom; (c) forced ow (one dimension of hydraulic freedom); and (d) stagnation (zero degrees of hydraulic freedom).


Chapter 2

zero hydraulic potential difference. Small eddies create a transitional mixing zone (Fig. 2.11b). Forced ow, as in water owing in a tube or a pipe. The impermeable walls of the pipe restrict the ow to the course of the pipe (one-dimensional degree of hydraulic freedom), with only one inow point and one outow point (Fig. 2.11c). Stagnation (zero ow), as in water in a closed bottle. The impermeable walls of the bottle completely block the mobility of the water (zero degrees of hydraulic freedom) and it stays at rest (Fig. 2.11d). The ow of groundwater is discussed in these terms in the following section.

2.12 Two Basic Experiments of Water Flow

Let us expose an empty aquarium to rain. The vessel will ll up and water will overow laterally toward the bases of drainage. The observation that the water is owing indicates that the water surface, or water table, is slightly inclined (Fig. 2.12) by the critical angle of ow. This angle is determined by properties of the water, mainly viscosity, which in turn is determined by salinity and temperature. If the vessel is exposed long enough

Fig. 2.12 A basic experiment in water ow: an aquarium exposed to rain. The vessel lls up and the additional rainwater overows. At a steady state, all the arriving rainwater ows laterally toward the bases of drainage, and the water at the bottom of the vessel is stagnant (dead volume).

Basic Hydrological Concepts


to rain, a steady state is reached at which new rain ows out laterally, whereas water at the bottom of the vessel remains at rest, forming a zone of stagnation (dead volume). Small eddies cause some mixing of water from the owing zone with water of the upper part of the stagnation zone, forming a transition or mixing zone. As a second experiment an aquarium is lled with sand and then exposed to rain (Fig. 2.13). Water inltrates through the sand, forming a saturated zone, and a water table that rises until lateral overow toward the edges of the vessel occurs. This critical angle of ow is slightly steeper in this experiment, as the water has to overcome the resistance to ow caused by the sand. At a steady state the rain inltrates vertically down through the heaped sand relief, performing free ow until the water table is reached, at which time the inltrating water switches to lateral ow. The presence of the sand impedes the formation of eddies, and the mixing zone is signicantly thinner as compared to the previous experiment, leaving a larger portion of the water beneath the base of drainage in a stagnant state. The phenomenon of lateral overow is of basic importance in groundwater systems: in steady-state conditions, typical for unconned groundwater systems, the rocks beneath the level of the terminal base of

Fig. 2.13 A second basic experiment in water ow: an aquarium lled and heaped with sand is exposed to rain. At steady state the rain inltrates along vertical downow paths (free ow) until a zone of lateral ow (overow) is reached. The water at the deeper part is stagnant. Eddies create a thin transition or mixing zone.


Chapter 2

drainage are lled with water that is under no potential energy gradient, blocking the downward ow direction for newly arriving water. Thus the hydraulic degree of freedom is only two-dimensional at the level of the base of drainage, causing lateral ow.

2.13 A Model of L-Shape Through-Flow Paths and Zones of Stagnation

Groundwater regimes are best understood by discussing entire groundwater drainage basins, that is, from the principal water divide to the terminal base of drainage, which in most cases is the sea (Fig. 2.14).

2.13.1 Unconned Permeable Systems

At the rst stage of the discussion let us assume that all the rocks in the system are highly permeable to a great depth beneath the level of the

Fig. 2.14 An entire groundwater system, from the water divide to the terminal base of drainage, built of permeable rocks. The following patterns of water motion are recognizable: (1) a through-ow zone with vertical ow paths that join a lateral ow path toward the terminal base of drainage; (2) a transition (mixing) zone; and (3) a zone of stagnation occurring beneath the level of the terminal base of drainage (zero hydraulic potential).

Basic Hydrological Concepts


terminal base of drainagethe entire system is unconned. The groundwater regime may be discussed by its following components:

Runoff. Precipitation falls over the surface of the system, partitioning between inltrating water and runoff. The runoff gets focused into the valleys and riverbeds, turning the latter into areas of increased inltration rates and thus increased recharge rates (Fig. 2.14).

Inltration and evapotranspiration. Inltrating water is partially returned to the atmosphere by evaporation of water that is retarded on the surface and in the soil zone. Another part of the inltrating water is returned to the atmosphere by plants by way of transpiration. Both effects, together called evapotranspiration, are effective to a depth of 13 m. In extra heavy rain or snowmelt events inltrating water moves beyond this depth and is then on its way into the saturated zone. The portion of water that enters the saturated zone is the recharge. Evapotranspiration returns distilled water into the atmosphere. The salts, dissolved in the original precipitation water, remain in the soil zone, and at the end of dry seasons some of these salts accumulate on the surface. The next rain event redissolves these salts, and eventually they are brought into the saturated zone. Thus recharge water is richer in atmospherically derived salts than the original precipitation. The factor by which the chlorine concentration in the recharge water is greater than its concentration in the respective precipitation serves as a semiquantitative tool to estimate the amount of water transferred to the atmosphere by evapotranspiration (section 6.15).

Recharge. The portion of inltrating water that reaches the saturated zone is the recharge. The following observations indicate occurrence of recharge: (1) a rise of the water table following rainy seasons, (2) measurable concentrations of tritium and other contaminants, indicating recharge during the last decades, (3) the continuous supply of water in shallow wells that sustain abstraction over hundreds and thousands of years.

Zone of through-ow. The term through-ow pertains to the section of the water cycle at which water is recharged, then ows through voids in the rocks, and eventually is discharged at a terminal base of drainage. This denition leaves out other modes of groundwater motion, which are not


Chapter 2

connected to ongoing recharge, for example, diffusion and migration due to compaction. Through-ow occurs in the zone of hydraulic potential differences, that is, between the topographic relief and the terminal base of drainage at which the hydraulic potential is zero (Fig. 2.14). The term terminal base of drainage is applied to emphasize that the level of nal drainage is meant, not an intermediate base of drainage such as a lake, a valley, or a river. The terminal base of drainage is in general the sea. Two major ow path directions prevail in the through-ow zone: vertical downow and lateral overow, or base ow (Figs. 2.13 and 2.14). The lateral ow path is dened by the location and altitude of the terminal base of drainage, and the slope of the lateral ow path is determined by the critical angle of ow. Recharged groundwater ows vertically down until it reaches the lateral ow zone. The situation is simple in coastal plainsthe recharge water ows vertically down (inltrates) through the aerated zone and the zone of lateral ow coincides with the water table. In mountainous terrains the zone of vertical downow reaches greater depths. The vertical downow paths and the lateral ow zone take the shape of the letter L, hence the name zone of L-shape through-ow paths, which differs from the U-shape ow paths model discussed in section 2.15. Zone of groundwater stagnation. At depths below sea level all the rock systems of the continents are lled with water to their full capacitythey are saturated. Being below sea level, the water stored in these rocks is under no hydraulic potential difference, and therefore this water does not owit is static, or stagnant (Fig. 2.14). This situation is similar to that of water stored in a tub, it cannot ow out, and hence is stagnant. Additional water reaching the tub overows. The same is observed in the sand-lled aquarium experiment (Fig. 2.13): after steady state is reached, all the new rainwater inltrates down to the level of the rim and ows out, whereas the deeper water remains static. A closer look at the zone of lateral base ow (overow). Overowing water ows laterally by the critical angle. This angle is determined by the water viscosity, which in turn is dependent on the temperature and concentration of dissolved ions. Groundwater ows laterally toward the terminal base of drainage at a critical angle that is determined by the hydraulic conductivity, or permeability, of the rocks (k) the water viscosity, which depends on the temperature (T), and the concentration of dissolved ions (i): Critical angle of flow water table gradient f fk; T; ig

Basic Hydrological Concepts


This topic warrants more experimental and theoretical work. Nonpumped wells in coastal plains reveal water tables that are at sea level at the seashore, while the water table is observed to be higher inland, portraying a water table surface that is inclined seaward by a gradient of 1 3 m/km. These water table gradients seem to reect critical angles of ow that vary because of variations in the rock conductivity (k). In coastal plains the observed water table reects the regional base ow and the gradient is the critical angle of ow. The zone of lateral base ow accumulates recharge water introduced over the surface. The ux, or amount of water owing at each section, increases from the principal water divide in the downow direction and reaches a maximal value at the drainage front. Thus the zone of lateral base ow has a certain thickness that is expected to grow toward the base of drainage. Through-owstagnation transition zone (mixing zone). Eddies cause some mixing of water from the through-ow zone with water in the underlying stagnation zone, resulting in the formation of a mixing or transition zone. Chemical, isotopic, and dating parameters are useful in determining the location and depth of the transition zone by tracing mixtures reected by these parameters, based on the compositional differences of the water from the two zones, and conditioned on access to adequate wells at various depths. A thickness of up to 50 m is assumed for a typical transition zone. A closer look at the zone of vertical downow paths. Local recharge ows vertically down until the zone of lateral ow is reached. In coastal plains the vertical ow zone is fairly thin, on the order of a few meters to a few tens of meters, and it clearly coincides with the aerated zone, and the water table signies the zone of lateral base ow. In mountainous regions the vertical ow paths are longer, and usually the higher the topographic relief is, the thicker is the zone of vertical downow. The following observations testify to the existence of vertical downow paths: . During the construction of the 11-km-long Mont Blanc tunnel, water was sampled at nearly 70 points of emergence (Fontes et al., 1979). The results are discussed in detail in section 10.7 and are portrayed in Figs. 10.13 and 10.14. The chemical composition reected the overlying rocks, and the stable hydrogen and oxygen isotopes reected the overlying topography (altitude effect), bringing the researchers to the conclusion that recharge water descended through fractures in a vertically downow direction. The height of the covering mountains is about 2300 m above the


Chapter 2

tunnel, and the latter is about 1300 m above sea level. Thus in this part of the Alps the vertical ow zone has a thickness of at least 2300 m, and the zone of lateral ow is below 1300 masl. The Mont Blanc tunnel study revealed additional information: tritium was found in all water samples in concentrations that indicated rapid downowin a matter of months to a few years. In addition, the tritium and chlorine concentrations varied signicantly between adjacent points of water collection, indicating that the downow occurs in fractures and other vertical ow paths that have restricted hydraulic interconnections. Flow of waters with different properties has since been studied in other tunnels, providing evidence for vertical downow paths in mountainous regions. Flow of water from fractures is often encountered in mines at different depths. Signicant variations in the water properties suggest locations in the downow zone. In contrast, in mines located in the lateral ow zone or in stagnant systems, uniform water properties are expected. Mountain slopes and escarpments are often with no springs, although they are recharged by precipitation. This is a clear indication that in such regions the recharge water ows vertically down until it meets a lateral ow zone at greater depth (Fig. 2.15). Karstic shafts manifest vertical downow paths.

Hydraulic connectivity in the vertical and lateral ow zones. Hydraulic connectivity is poor in the vertical downow zone and signicantly higher in a lateral base ow zone. Downow paths in fractures and in porous material have restricted hydraulic interconnections, as has been well demonstrated in the mentioned study of water at the Mont Blanc tunnel. In mountainous terrains this results in some ambiguity as to the conguration of the water table. Recharge water ows down in a wide range of velocities, varying among fractures and between fracture ow and porous ow. Furthermore, karstic systems (section 2.9) contain in the dry season air pockets that ll up in the high ow season (Herzberg and Mazor, 1979). Disconnected setups of the downow paths reveal: . . . . Different heights of the water table in neighboring wells Different seasonal uctuations of the water table in adjacent wells Selectivity in the propagation of contaminants Different water properties in nearby wells and springs

Basic Hydrological Concepts


Fig. 2.15 Many escarpments and mountain slopes have no springs, especially in semiarid regions. This shows that in such regions the vertical downow paths of the local recharge water are relatively deep, meeting a lateral base ow zone that is situated deeper than the base of the escarpment.

The hydraulic connectivity is much better along the ow paths of the lateral ow zone. This is best demonstrated on coastal plains: groundwater ows from the mountain foothills toward the sea, and along these ow paths local recharge water is added and intermixed.

Evidences for the existence of hydraulically isolated conned groundwater systems. Adjacent wells in deep artesian systems are often observed to differ in (1) their lithological sequences, indicating that abstraction is from different aquifers that are either stacked one on the other or are laterally adjacent; (2) the chemical composition of the water, indicating that efcient hydraulic barriers prevent the different waters from intermixing; (3) the isotopic composition of the water, indicating recharge under different climatic regimes; (4) the concentration of the isotopic age indicators, demonstrating recharge at different times; (5) the frequently observed high isotopic ages (more than 25,000 years, indicated by a lack of measurable 14 C, and more than 106 years, indicated by a lack-of atmospherically produced 36Cl), indicating cutoff from ongoing recharge; and (6) the hydraulic pressures, indicating that the various wells tap distinct aquifers. Arguments of this kind have been used to demonstrate the existence of trapped groundwaters in the Great Artesian Basin, Australia (Mazor and Nativ, 1992, 1994; Mazor, 1995), the Dead Sea Rift Valley (Mazor et al., 1995), and the Ramon National Geological Park, Israel (Fridman et al., 1995).


Chapter 2

Fossil through-ow systems. Trapped groundwater usually occurs in conned systems that are deeply buried in subsidence basins and rift valleys, as demonstrated by the list of observations discussed in the previous chapter. These stagnant systems often sustain self-owing (artesian) wells. The water encountered in these wells has isotopic compositions that establish with certainty a meteoric origin. Hence, the trapped water systems are fossil through-ow systems that underwent subsidence, followed by accumulation of sealing rocks and the formation of new through-ow systems that eventually were buried as well. Continental sediments, accumulated in most basins, are characterized by frequent lithological changes, vertically and laterally, including facies changes and interngering. These environments make room for a multitude of separated aquifers, a tendency that is further accentuated by tectonic deformations. The age of groundwaters trapped in sedimentary basins is expected to be between the age of the hosting rocks and the age of the subsidence stage that caused the hydraulic isolation. The four basic modes of water ow, discussed in the previous section, are well observed in groundwater systems: free ow (three-dimensional degrees of hydraulic freedom) in the vertical downow zone; overow (twodimensional degrees of hydraulic freedom) in the zone of lateral base ow; forced ow (one-dimensional degree of hydraulic freedom) in fractures and karstic channels; and stagnation (zero degrees of hydraulic freedom) in groundwater traps. These basic modes of groundwater ow are the essence of the presented model of L-shape through-ow paths and zones of stagnation.

2.13.2 Effect of Hydraulic Barriers in the ThroughFlow and Stagnation Zones

The through-ow zone has so far been described in a simplied mode, assuming all the hosting rocks are homogeneously permeable. Deviations from the simplied L-shape of the ow path are caused by the presence of hydraulic barriers, such as clay and shale, that may in certain places block the downow and create local perched water systems and springs (Fig. 2.16) or cause steps in the path of the lateral ow zone. But the overall L-shape is generally preserved, as the water of perched systems nds pathways to resume the vertical downow direction.

2.13.3 Through-Flow and Stagnation Zones: The Global Picture

Figure 2.17 portrays a global picture: through-ow systems prevail above sea level; stagnant trapped systems dominate beneath sea level (along with

Basic Hydrological Concepts


Fig. 2.16 A lense of impermeable rock creating a local perched water table and a spring; an aquiclude sealing off a stagnant zone, turning it into a conned system; and karstic features.

Fig. 2.17 A global picture. At depths above sea level through-ow systems prevail, near sea level exists a transition zone with both through-ow and stagnant systems, and beneath sea level stagnant groundwater systems prevail.


Chapter 2

petroleum traps); and a transition zone exists in between. The volume of water stored in stagnant systems seems to match the volume stored in through-ow systems.

2.14 Deep Basin Compartments of Pressurized Water, Petroleum, and Geothermal Fluids
A large number of articles deal with different aspects of abnormal pressures observed in uid-containing rock compartments (Martinsen, 1994). Recently, there appeared a comprehensive collection of 30 articles dealing with basin compartments and seals (edited by Ortoleva, 1994). The topic is presented by Ortoleva and Wescott (1994): In the early 1970s, Powley and Bradely recognized that basins worldwide exhibited an unexpected degree of hydrologic segregation. They observed regions of a sedimentary basin that were isolated from their surroundings by a relatively thin envelope of low-permeability rock and had an interior of sufciently high permeability to maintain a consistent internal hydrostatic uid pressure gradient. They named these regions uid (or pressure) compartments. Pressure compartments have several remarkable features. First, their internal uid pressures may greatly exceed or be signicantly less than any regional topographically controlled hydrologic head or drain. Thus, their internal pressure cannot be explained by connection to another similarly pressured source or sink region. Next, their bounding rock often does not follow a single stratigraphic unit but transverses several units. This contradicts conventional thinking, wherein low permeability beds such as shale, salt or bedded anhydride serve to separate geopressured regions above and below but there are no recognized lateral boundaries. Furthermore, this surrounding shell was such an efcient barrier to uid ow that it could retain very large potentiometric pressure heads over geologic timei.e., the hundreds-million-year time frame. They thereby termed the surrounding rock a seali.e., a relatively thin region of rock at the top, bottom, and all sides that can retain pressure gradients on time scales very much longer than that required for dissipating nonhydrostatic gradients within the interior. The fact that these compartments often contained large reserves of oil and gas made them very interesting.

Basic Hydrological Concepts


The size of identied pressurized compartments is reported to vary from small-scale structures, 110 km across, to mega-scale compartment complexes of hundreds of kilometers across; they have been reported from depths of 20005000 m; and potentiometric heads were mostly between the local (theoretical) hydrostatic head and the local lithostatic head. Multiple compartments are distributed vertically and laterally. The pressurized compartments are regarded to be closed chemical systems as no throughow occurs in them. Examples of large-scale hydraulically isolated compartments were reported (in Ortoleva, 1994) from Mississippi salt basin, Oklahoma, Kansas, Texas, Louisiana, Colorado, Nebraska, New Mexico, California, Nova Scotia, Alberta Basin, Caspian Sea, Black Sea area, Yugoslavia, Guatemala, Australia, Indonesia, and the Persian Gulf. We would like to add the Great Artesian Basin, Australia, as an example of a megacompartment that is divided into many small-scale subcompartments. The Great Artesian Basin is divided into a shallow unconned system, underlain by Tertiary rocks that host medium-quality groundwater, beneath which is the Cretaceous marine rock sequence that hosts mainly artesian saline groundwater, and beneath that is the Jurassic continental rock sequence that hosts fresh artesian groundwater (the main exploited system). Each of these large-scale systems is divided into numerous small-scale compartments, recognizable by their different properties (Mazor, 1993, 1995). Bradley and Powley (1994) suggest, The primary cause of either pressure or ow is epirogenic movement, with erosion or deposition, which changes the temperature, stress, and pore pressure in the system, which in turn, affect the diagenesis in the system. The phenomenon of hydraulically sealed, isolated, and pressurized uid containing compartments has been observed in structures over 2000 m deep studied in connection with oil and gas prospecting. The concept is, in a way, a newcomer to the oil exploration community and is regarded as an unexpected observation. This point is reected, for example, in the terms abnormal pressure or overpressure, applied to indicate pressures greater than the originally expected hydrostatic pressure.

2.15 The Traditional Model of U-Shape Flow Paths

Figure 2.18 depicts a cross-section of a model that has been much quoted in the hydrological literature from Hubbert (1940) to most recent textbooks and articles. The modeling is restricted to a valley ank in a small drainage basin. The cross-section is through half a valley, from a local divide to a nearby low-order valley. The three marked planes are assumed in the model to be impermeable (no water is assumed to ow across the vertical planes


Chapter 2

Fig. 2.18 A cross-section of a much-quoted model (following Freeze and Cherry, 1979, who cited Hubbert, 1940). The surface is described as undulating in a mode that can be expressed by a simple mathematical equation, and the water table is assumed to follow topography in a xed mode. The stippled section describes a water system from a low-order divide to a nearby low-order valley; the thick lines mark there impermeable planes that are an intrinsic part of the U-shape ow paths model, enlarged in Fig. 2.19. The cross-section emphasizes topographic undulations and disregards the location of the terminal base of drainage and the location of the main water divide.

that are marked beneath the local divide and beneath the valley, and an impermeable horizontal rock bed is assumed at some depth). The water table is modeled as a moderated replica of the topography, which in turn is assumed to be expressible by a simple mathematical equation. Figure 2.19 shows a more detailed cross-section of the modeled area. The system is assumed to be composed of homogeneous permeable rocks. Equipotential lines, calculated by the model, were computed, and lines of force, or ow lines, were deduced perpendicular to the former. These model calculations, incorporating Darcys law, deduced U-shape ow paths that are composed of zones of recharge (points C, E, G, and H in Fig. 2.19) and zones of discharge (points A, B, D, and F in Fig. 2.19) closely coinciding with topographic highs and lows, respectively. The resulting ow lines were divided (Toth, 1963) into three ow regions: local, intermediate, and regional. Realistic dimensions for the model were suggested to be a width on the order of 7 km and a depth on the order of 3 km, and in a 1995 paper, Toth suggested the model to represent entire sedimentary basins. The early U-shape ow paths models assumed homogeneous permeable rocks for the entire system, but this restriction was later removed by the argument that all rocks are permeable to some degree. Thus the road was paved to apply the U-shape model to entire basins. A basic outcome of the U-shape ow paths model and its many derivations was that all groundwater systems were discussed in terms of

Basic Hydrological Concepts


Fig. 2.19 A more detailed cross-section of the U-shape model area shown in Fig. 2.18 (condensing several gures of Toth, 1963, 1995). Groundwater ow paths deduced by the U-shape ow paths model are marked with arrows denoting ow directions. Three ow zones have been concluded: local, intermediate, and regional, with alternating points of discharge (e.g., points A, B, D, F) and points of recharge (points C, E, G, H). The symmetry of the suggested ow lines, centered in the modeled box, reveals that they are a direct outcome of the assumption of the three impermeable ow planes.

through-ow, at various ow velocities, and stagnant (static) groundwater was disregarded.

2.16 Discussion of the U-Shape Flow Paths Model

As mentioned, the basic U-shape model, depicted in cross-section in Figs. 2.18 and 2.19, assumes three impermeable planes and discusses onehalf of a land unit that is hard to identify in nature. Let us examine this approach in the frame of an entire groundwater drainage basin as shown in Fig. 2.20. The assumption of the three impermeable planes loses ground because the modeled small land cell is part of a larger through-ow system, with recharge inputs from higher altitudes and through-ow toward the terminal base of drainage. The local, intermediate, and regional ow regions, depicted in Fig. 2.19 as an outcome of the U-shape model, are hydraulically nonlogical. There is


Chapter 2

Fig. 2.20 The modeled box of Figs. 2.18 and 2.19, plotted on a regional crosssection from a major watershed to the terminal base of drainage. The assumption of three impermeable planes is groundless, as discussed in the text.

no physical process that determines that water recharged at the right end of the modeled half basin (point H in Fig. 2.19) will have the deepest (regional) penetration and discharge at the left corner (point A in Fig. 2.19), that water recharged in the next location (point G in Fig. 2.19) will penetrate to intermediate depths, and in a symmetrical mode discharge at the left of the model (point B in Fig. 2.19), while shallow (local) circulation of water recharge and discharge will occur only at the center of the modeled section (points CF in Fig. 2.19). The suggested ow paths in Fig. 2.19 are seen to be a freak of the assumed three impermeable planes. If the principal premise of the model, namely, the existence of the three impermeable boundaries, is wrong, then the whole model collapses and the discussion could be terminated at this point. But the notion of deep U-shape ow paths prevails and warrants discussion of the feasibility of its conclusions. Presentations of the U-shape model in the literature do not specify the location of rain or snowmelt water and do not discuss the resulting recharge distribution. Commonly, rain falls over the entire area of an unconned system, as depicted in the cross-section shown in Fig. 2.20. Runoff, too, is all over, but with an uneven distribution, as it runs fast from the topographic highs and accumulates and ows relatively slowly at the topographic lows. Thus recharge takes place all over the surface, but is intensied in the

Basic Hydrological Concepts


valleys, contrary to the discharge in valleys concluded by the U-shape model (e.g., points B, D, F, G, and H in Fig. 2.19). Various researchers deduced that the ow regime is most sensitive to the topography: in at terrains regional ow systems were concluded to prevail, whereas in homocky terrains, numerous shallow ow regions have been concluded to be superimposed on the suggested regional system (Freeze and Witherspoon, 1967, adopted in various following publications). This is another articial outcome of the U-shape model, as the depth of the ow paths is determined by the level of the terminal base of drainage, and the latter is never discussed in the U-shape model. A major shortcoming of the U-shape ow paths model is the forcing of water down to below the level of the base of drainage, and then forcing it up at hypothetical discharge locations (Fig. 2.19). Above the level of the terminal base of drainage, in the through-ow zone, all water particles ow downhill, under the force of gravity, the through-ow zone occupying the space in which hydraulic potential differences prevail (Figs. 2.142.16). Thus, no water particle has to push away other particles along its ow path, as they move by themselves, and energy consumption goes to overcome friction alone. In contrast, beneath the level of the terminal base of drainage, no hydraulic potential exists and the water particles do not move by themselves. Hence, to make water ow in a U-path beneath the level of the base of drainage, other water particles have rst to be pumped or pushed up toward a discharge region, and this necessitates a great source of energy, which does not exist. Evoking such a ow means to claim the nding of a perpetual mobile process. Deep basinwide through-ow models are based on the assumption that water-conducting rock strata, or aquifers, stretch uninterrupted for hundreds of kilometers and serve as through-ow ducts. Through these aquifer ducts water is suggested to ow from recharge areas at marginal outcrops. The aquifer ducts are commonly dened in accordance with regional stratigraphic units (Fig. 2.21). However, stratigraphic units incorporate many alternations of permeable and impermeable rocks, constituting a multitude of potential aquifers (Fig. 2.10). Hence, according to the basinwide through-ow model, a multitude of separate ducts and marginal recharge areas must exist, contrary to eld observations. The model of stagnant groundwater traps ts the observations much better (Mazor and Nativ, 1994; Mazor, 1995). Compaction caused by the weight of overlying rocks is called upon to explain the water pressure in deep-seated artesian aquifers (Mazor, 1995). Compaction counteracts through-ow in deep aquifers, as it causes collapse features, and pressurizes the entrapped water. If through-ow would take place, the open ends of the hypothetical aquifer ducts would serve as


Chapter 2

Fig. 2.21 An example of a cross-section depicting hundreds of kilometers across a subsidence basin, with stratigraphic units assumed to act as through-ow ducts (the Great Artesian Basin, Australia) (following Seidel, 1980).

pressure vents and no high pressures would be observable. The very fact that the artesian systems are pressurized indicates they are closed systems and not open ones.

2.17 Summary of Modes of Groundwater Flow

The discussed phenomenological model of L-shape through-ow paths and zones of stagnation may be summarized in light of the degrees of hydraulic freedom for recharge input and for ow as presented in section 2.11:
Mode of ow Free ow Lateral overow Forced ow Stagnation Degrees of hydraulic freedom Three-dimensional Two-dimensional One-dimensional Zero-dimensional Flow and direction Vertical downow Lateral base ow Karstic conduits, joints Groundwater traps

2.18 Summary Exercises

Exercise 2.1: Match the observations to the concluded processes or existing systems:

Basic Hydrological Concepts


Observation 1. A well has an upper dry section 2. A well has a lower part lled with water 3. The water table often rises seasonally 4. The water table often falls seasonally 5. The upper soil dries up seasonally 6. Plants depend on rain or irrigation

Process or system A. Transpiration B. Recharge C. Aerated zone D. Discharge E. Evaporation F. Saturated zone

Exercise 2.2: Groundwater is visualized by some people as occurring in underground lakes and rivers. Looking at a well we nd in it wateris this an indication that the well taps such a lake? Exercise 2.3: In a year with twice the average annual rainfall, the resulting recharge is signicantly greater than twice the average annual recharge, a phenomenon most evident in arid regions. Why? Exercise 2.4: In light of the previous question, is the average annual rain a sufcient representative parameter to assess recharge? Is another parameter needed? Exercise 2.5: In the course of drilling a borehole, water was encountered rst at a depth of 20 m and again at a depth of 54 m. Can you describe the local aquifers in terms of being phreatic or conned? Which additional data would you like to have to further check your conclusions? Exercise 2.6: The Banias Spring issues at the foot of snow-covered Mt. Hermon. Which measurements are recommended in order to nd out whether this is a karstic spring fed mainly by snowmelt? Exercise 2.7: What is the denition of groundwater age? Where is there a better chance to determine meaningful water ages, in unconned systems or in groundwater traps?


3.1 Lithology and Its Bearing on Water Composition

The composition of rocks and soils has a direct bearing on the quality of water. Hydrochemically a rough classication into three rock groups seems practical: . . . Rocks in which fresh groundwater is common, that is, rocks that contribute extremely small amounts of salts to the water Carbonate rocks that contribute dissolved matter but maintain good potable quality Rocks that enrich the water with signicant amounts of dissolved salts, often making them nonpotable

The lithological parameter is only one of several parameters that control groundwater quality. Other factors include evaporation at the surface prior to inltration, transpiration, wash-down of sea spray, and reducing conditions in the aquifer, connected to H2S production. Water moves underground, and its salt or mineral content is determined by all soil and rock types it passes through. Thus, occasionally, saline water may be encountered in rocks that by themselves do not contribute soluble salts.

3.1.1 Rocks that Preserve High Water Quality

Pure sandstone, rich in quartz grains and with little or no cement, may host very fresh water with little addition to the salts brought in by recharging rain (Table 3.1). Other rocks hosting fresh water are quartzite (sandstone

Geological Data Table 3.1 Lithological Imprints on Groundwater Composition Rock Sandstone Limestone Dolomite Granite Basalt Schist Marl Clay and shale Groundwater composition



Low salinity (300500 mg/l); HCO3 major anion, Na, Ca2, Mg2 in similar amounts; good taste. Low salinity (500800 mg/l); HCO3 major anion, Ca2 dominant cation; good taste. Low salinity (500800 mg/l); HCO3 major anion, Mg2 equals Ca2; good taste. Very low salinity (300 mg/l); HCO3 major anion, Ca2 and Na major cations; very good taste. Low salinity (400 mg/l); HCO3 major anion; Na, Ca2, Mg2 equally important; good taste. Low salinity (300 mg/l); HCO3 major anion; Ca2 and Na major cations; good taste. Medium salinity (1200 mg/l); HCO3 and Cl major anions, Na and Ca2 major cations; poor taste but potable. Often containing rock salt and gypsum. High salinity (900 2000 mg/l); Cl dominant anion, followed by SO2 ; Na major 4 cation; poor taste, occasionally nonpotable. High salinity (20004000 mg/l); SO2 dominant anion; Ca2 4 dominant cation, followed by Mg2 or Na; bitter, nonpotable.

cemented by silica), basalt, granite, and other igneous rocks (Table 3.1). The total dissolved salts in the water encountered in these rocks is often in the range of 300500 mg/l.

3.1.2 Carbonate Rocks

Limestone and dolomite commonly host water with 500800 mg/l total dissolved salts, mainly Ca(HCO3)2, in the case of limestone, and (Ca,Mg)(HCO3)2 in the case of dolomites. The relevant chemical water rock interactions are discussed in section 6.8. Water encountered in limestone and dolomite is generally tasty and of high quality.

3.1.3 Evaporites: Gypsum and Salt Rock

Gypsum (CaSO4 ? 2H2 O) is formed mainly in lagoons (semiclosed shallow water bodies, mainly along oceanic coasts) that are subjected to high degrees of evaporation. Seawater evaporated to one-third of its original volume precipitates gypsum (or anhydritea water-poor variety of gypsum).


Chapter 3

Groundwater in contact with gypsum rock dissolves it, along with accompanying salts, reaching 10002600 mg/l of SO4, along with Cl, Ca, Mg, and Na, the total dissolved salt content reaching 20004000 mg/l (Table 3.1). The taste of such water is bad, mainly bitter. Water with up to 600 mg/l SO4 can be consumed in an emergency, but higher concentrations will cause thirst rather then quench it. Stock may, however, drink such water. Rock salt (NaCl) is formed by even higher degrees of evaporation, also in lagoons and closed lakes. Seawater is saturated in NaCl when evaporated to one-tenth of its original volume. Water coming in contact with rock salt dissolves it, becoming rich in NaCl. Water in contact with rock salt is brackish or brine, nonpotable water, with salinities as high as (brackish water) or higher (brine) than seawater.

3.1.4 Clay and Shale Hosting Gypsum and Rock Salt

Clay and shale are hydroaluminum silicates that by themselves do not add salts to the water that comes in contact with them. However, clay and shale often contain veins and nodules of gypsum, pyrite, and rock salt. Clay and shale are impermeable and form aquicludes rather than aquifers (sections 2.3 and 2.4), but because of the high solubility of gypsum and especially rock salt, groundwater in contact with clay and shale at the base of aquifers often gets saline and is of poor quality.

3.1.5 Lithological Considerations in Well Location and Design: The Water Quality Aspect
Selection of well sites is done on the basis of several aspects, water quality being a major one. Thus a thorough knowledge of the lithological section of candidate well sites is of prime importance. Gypsum and rock salt should be avoided in any case. Aquicludes of salinizing rocks, such as clay and shale, have to be avoided, either by terminating the wells or their perforated sections above the clay or shale layer, or by sealing the well at the aquiclude section, avoiding entrance of poor quality water (Fig. 3.1).

3.2 Properties of Geological Materials and Their Bearing on Recharge and Groundwater Storage
Inltration of recharge water occurs through interconnected pores, open joints and ssures, or combinations of these features (Fig. 3.2). In contrast, rocks rich in pores that are too small or isolated from each other, nonporous rocks, and rocks with no open ssures are inefcient for inltration and

Geological Data


Fig. 3.1 Two aquifers of nonsaliferous rocks, separated by an aquiclude of clay with gypsum and salt rock. (I) fully perforated and producing saline water; (II) stopped at a safe distance above the clay, abstracting good water from the upper aquifer alone; (III) sealed for several meters above and below the clay bed, producing good water from both aquifers.

recharge. The same principles hold true for water movement and water storage in aquifers. Rocks with open interconnected pores and open interconnected ssures are best for recharge and storage.

3.2.1 Materials with Open Interconnected Pores

All granular rocks are rich in interconnected pores. The most common types are sand and sandstone. Their recharge and storage quality increases with the grain size. Cement (carbonate, silica, iron oxide) reduces the pore volume and, in extreme cases, may result in an impermeable sandstone (however, cemented sandstone tends to fracture). Conglomerate (a rock

Fig. 3.2 Modes of water inltration. (I) porous texture with no cement between the grains, high inltration rate and water storage capacity; (II) nonporous texture with open interconnected ssures, good inltration and storage capacity; (III) partially porous texture with interconnected ssures, inltration and water storage are possible in two modes: through noncemented interconnected pores and through ssures.


Chapter 3

made up of pebbles of rocks) is an extreme case of a granular rock and, if noncemented, has excellent recharge and storage properties.

3.2.2 Materials with Open Interconnected Fissures

All brittle rocks tend to be fractured to different degrees. The joints and ssures may in certain cases be somewhat enlarged by dissolution, but they may also be clogged with clays produced by weathering. Thus it is not enough to know the rocks that constitute the terrain in studied areas, you must also know their degree of fracturing and weathering. An extreme case of open interconnected conduits is manifested by limestone and dolomite in karstic terrains, as described in section 2.9.

3.2.3 Materials with Poorly Connected Pores

Clay and shale have a large number of minute pores, totaling up to 55% of the rock volume. Yet these pores are poorly interconnected, resulting in very low permeability or impermeability (section 2.7). Clay and shale signicantly slow inltration and serve as aquicludes.

3.2.4 Materials with Isolated Fissures

Metamorphic rocks are rich in open foliation fractures and ssures, but these are isolated or poorly interconnected. Such rocks make poor recharge terrains and poor aquifers. These rocks are occasionally fractured by tectonic processes, improving their inltration and storage properties.

3.2.5 Studying Rocks for Their Conductivity or Recharge and Storage Capacities
Rock properties should be examined at as many outcrops as possible, looking for friability, cementing, degree and nature of fractures and dissolution conduits, and animal burrowing (Figs. 2.3, 2.4, 2.8, and 3.2). However, one should bear in mind that rocks at exposures are altered by weathering and joint formation due to stress release and thus may poorly represent the rocks at depth. Similar observations may be conducted on drill cores, but these are expensive and their record is limited in size. Laboratory tests on cores provide semiquantitative data on the nature of rock pores and ssures and conductivities. Another way to determine the relevant rock properties is to examine the properties of groundwater in springs and wells. Young water ages and seasonal variations of discharge and temperature indicate rapid passage through high conducting rocks, whereas high water ages and constant

Geological Data


discharge and temperature indicate retardation and low conductivity, at least along part of the water system.

3.3 Layering and Its Control on Groundwater Flow

Many rock types have a layered structure, individual rock layers varying in thickness from a few centimeters to tens of meters. Layered rocks include marine sediments, most continental sediments, lava ows and volcanic ejecta, and intrusive sills. The hydraulic properties vary from one rock layer to another, often resulting in abrupt changes along the vertical axis. In terms of the permeability coefcient (k) the lateral coefcient (kx) may signicantly differ from the vertical coefcient (kz). The alternation of aquifers and aquicludes results from the layered structure of different rocks, and the occurrence of springs is often controlled by the layering of rocks. Fissures may be restricted to individual rock layers or cross several rock beds, in which case water ow is improved, mainly in the vertical direction.

3.4 Folded Structures and Their Bearing on Flow Direction, Connement, and Entrapment
Water ows from high to low points and prefers the path of least resistance. In regions built of bedded rocks, tilting may be a prime factor determining ow direction (besides topographic gradients), as shown in Fig. 3.3. Among folded structures, synclines are important because they often gather water from neighboring anticlinal structures (Fig. 3.4). Hence an understanding of the tectonic regime of a well target area is essential. Flow directions deduced

Fig. 3.3 Factors controlling the ow direction of groundwater. (I) porous rock; water direction is determined by topographic gradients alone; (II) a tilted impervious rock bed deviates direction of water ow.


Chapter 3

Fig. 3.4 Groundwater accumulating in a syncline. Well I, located at the syncline, has a signicantly higher production then well II, located in an adjacent anticline. The lowering of the water table, due to pumping, will cut well II dry in a short time. On the other hand, fracturing in the crest of an anticline occasionally makes these locations better places for water supply.

from tectonic and topographic arguments should be checked by other methods, as outlined in the following chapters. Conned aquifers (section 2.8) are rare in tectonically undisturbed regions with horizontal rock beds (Fig. 3.5). Tilting of the aquifer and aquiclude sandwich makes room for the formation of conned aquifers. It provides each case with a recharge outcrop section, forming a phreatic aquifer (section 2.8) and a conned section fed by the former (Fig. 3.6). Subsidence structures are common. They are formed by the gradual lowering of rock strata, forming basin shapes. Two major processes operate during subsidence: burial of older rock beds and accumulation of new sediments at the surface forming new rock beds or lenses that eventually get buried as well, the water stored in them becoming trapped (Fig. 3.7).

Fig. 3.5 Horizontal rock beds often allow for the formation of only one recharged (phreatic) aquifer, the rst aquiclude preventing recharge water from reaching lower potential aquifers.

Geological Data


Fig. 3.6 Tectonic tilting of rock strata provides the necessary condition for the formation of a partially conned aquifer. A phreatic section, located at the outcrop of the rock bed, serves as recharge intake area feeding the conned section in cases where the inclined rock bed has a drainage outlet at its lower end enabling throughow (which is a rare case).

Subsidence structures may be narrow, such as rift valleys and intermountain basins (ranges and basins) that are tens of kilometers wide, hundreds of kilometers long, and hundreds to thousands of meters deep, and in other cases subsidence structures may be hundreds to thousands of kilometers across and a few thousand meters deep. Subsidence structures often host traps of stagnant groundwater bodies. The groundwater entrapment is caused by several processes: (1) burial to beneath sea level, that is, burial into a zone of zero hydraulic potential and hence a zone of stagnation; (2) coverage by younger sediments

Fig. 3.7 Stagnant conned systems are former (fossil) through-ow systems (1) that got buried beneath the level of the terminal base of drainage and (2) were covered by new rock systems that eventually got buried. System (3) is presently active as a through-ow system.


Chapter 3

that include clay and shale that cut off the groundwater traps from active recharge; (3) frequent changes in lithology (e.g., interngering, which is common in continental sediments that ll subsidence structures), hydraulically insulating individual rock bodies, turning them into groundwater traps; and (4) tectonic activity that causes faulting, folding, and thrusting accompanied by squeezing of plastic impermeable rocks (e.g., clay and shale) into gaps formed in the competent aquifer rocks, causing further hydraulic isolation of water-bearing rock bodies.

3.5 Faults Controlling Groundwater Flow

Faults cause discontinuities in rock sequences and thus control groundwater ow. A fault may set high-conducting aquifer rocks against impervious rocks, resulting in water ascent along the fault zone and formation of springs marking the fault line (Fig. 3.8). Occasionally groundwater continues in its general ow path across a fault, but in different rock beds (Fig. 3.9). Another fault controlled example is the gathering of groundwater into rock beds of a rift valley (Fig. 3.10). The above examples look simple, but in reality subterranean structures are often hard to recognize, and physical, chemical, and isotopic tracers are recruited to assist interpretation. Fault zones may be open and highly conductive, or they may be sealed by mineral precipitation, forming hydraulic barriers.

Fig. 3.8 A fault has placed a high conducting aquifer against an igneous rock of low permeability. Water ascends along the fault zone, forming a line of springs. Only part of the faults are open and conduct groundwater ow; others are clogged by compression and/or mineralization.

Geological Data


Fig. 3.9 Groundwater changing aquifer beds along the ow path due to strata displacement by a fault.

3.6 Intrusive Bodies Inuencing Groundwater Flow

Igneous intrusive bodies occasionally are observed to act as subterranean barriers or dams. Good examples are dikes (Fig. 3.11), sills (Fig. 3.12), and stocks. Fresh igneous rocks are nonpermeable, but with time they become fractured and may be somewhat conducting. Clay-rich weathering products may ll such fractures and improve their sealing properties. In the case of dikes, water gets dammed on the upstream side (Fig. 3.11). When placing a well near a dike it is essential to recognize the existence of the dike, although it is often concealed by alluvium. Lack of such information may result in a dry borehole drilled on the downow side of the dike.

3.7 Hydrochemical and Isotopic Checks of Geological and Hydrological Models

Geological models are an independent entity and an essential part of hydrological models. Geological models deal with rock sequences (candi-

Fig. 3.10

Runoff and groundwater owing into a rift valley.


Chapter 3

Fig. 3.11 A dike intersecting the ow of groundwater and acting as a subsurface dam. The water table is higher on the upstream side, providing a promising site for drilling a well.

date aquifers and aquicludes), rock properties (in terms of their potential inuence on the quality of hosted groundwater), existence of preferred ow paths (karstic features, open fractures and faults), identication of subsidence structures, and identication of hydraulic barriers (intrusive bodies and clay or shale squeezed into and around tectonically shaped rock bodies). However, geological data are scarce and of a fragmented nature, seldom leading to a unique model solution. Hence, geological conclusions, or suggestions, should always be checked against hydrochemical and isotopic observations.

Fig. 3.12 A sill intruded between carbonatic rock beds forming a local aquiclude. Weathering into clay minerals may improve the sealing capacity of a sill.

Geological Data


Similarly, hydrological models, based on precipitation distribution, topographic relief, location of the terminal base of drainage, hydraulic head data, and geology are also of a fragmented nature and seldom lead to a unique model solution. The situation may be signicantly improved by the application of hydrochemical and isotopic checks, as discussed below.

3.7.1 Concentration of Conservative Dissolved Ions Serving as a Check of Hydraulic Connectivity

Hydraulic connectivity is a basic premise in the construction of groundwater ow paths, calculation of ow velocity, and computation of travel time and water age. Groundwater is suggested to ow along a hydraulic gradient that is deduced from hydraulic head data obtained from measurements in wells and springs (section 4.3). These suggested gradients are valid only if the measured wells are all hydraulically interconnected (section 6.5). In other cases groundwater is assumed to ow in unconned and conned aquifers, described as continuous and effective ducts, based on geologically deduced congurations. However, the geological data are fragmentary and are often based on mapping or stratigraphic, rather than lithologic, units. Independent methods are needed to check the crucial assumption of hydraulic connectivity in every case study and for every geological and hydrological model. There are essentially only two sources of chloride in groundwater: sea spray in the form of atmospheric (airborne) salts, and dissolution of halite in the limited number of cases where this mineral is present in the rocks passed by the water. Chloride is a conservative ion; it does not participate in water rock ion exchange interactions, and once it enters the groundwater there is no process that can remove it (section 6.12). Other conservative ions of interest in the present context are bromide and lithium. Water that comes into contact with halite dissolves it rapidly, and in a matter of days becomes saturated, the water reaching a chloride concentration of more than 180,000 mg/l. Common groundwaters contain chloride in the range of 10 1000 mg/l and are therefore undersaturated with respect to halite, indicating no halite is present in their respective rock systems. Thus the common source of chloride in groundwater is atmospheric and its concentration is by and large controlled by the amount of water lost by evapotranspiration prior to entry into the saturated zone. In the saturated zone the chloride concentration stays constant unless mixing of different water types occurs. A chloride concentration that decreases along a suggested groundwater ow direction indicates the suggested ow path model is not valid, as there is no process that can reduce


Chapter 3

the chloride concentration. In such a case the assumption of hydraulic interconnection between wells that tap the same water body is wrong, and one deals with separate aquifers (Fig. 3.13). An abrupt increase in the observed chloride concentration along a suggested groundwater ow path indicates as well that the assumption of hydraulic connectivity is invalidated (Fig. 3.14). Certain springs are fed by a mixture of water from a deep aquifer, ascending along a fault plane, and water from a shallow aquifer (Fig. 3.8). The intermixing waters have different compositions, and the mixing ratios vary seasonally. Repeated analysis of a spring that reveals varying composition indicates an outlet that drains two (or more) distinct aquifers.

3.7.2 Concentration of Age Indicators as a Check of Hydraulic Connectivity

Groundwater in unconned systems receives recharge over the entire surface and, hence, is expected to have a recent age (section 10.4). If a well included in a model of an unconned system reveals an absence of tritium, the model has to be modied to include a conned aquifer beside the unconned one (Fig. 3.14). Water in a conned aquifer is expected to have the same age or reveal a certain age increase downow. However, if the age varies suddenly between adjacent wells, for example, gets younger in the downow direction, the connectivity assumption is disproved (Fig. 3.13).

Fig. 3.13 A transect through wells that display a gradually lower water table, yet the chloride concentration is lower in the well with the lower water table. In this case the explanation is that the wells tap different aquifers and are not hydraulically interconnected. Tritium values further clarify the picture: wells I and II tap a conned aquifer, whereas well III taps a phreatic through-ow system.

Geological Data


Fig. 3.14 A transect through wells that display a gradually lower water table, yet the chloride concentration is distinctly higher in the well with the lowest water table. This indicates that wells I and II are interconnected, but well III taps a different aquifer. Tritium data provide additional insightwells I and II tap a through-ow system; well III taps a conned aquifer.

3.7.3 Seasonal and Abstraction-Induced Changes in Water Composition as a Check for Interconnection of Two or More Aquifer Systems (Mixing of Groundwaters)
Models based on geological observations have no way to indicate the number of water types involved in a studied systemcommonly a single groundwater type is assumed to prevail. Hydraulic models, based on water table and hydraulic head measurements, are similarly shorthanded and cannot detect intermixing of different groundwater types, a phenomenon that requires hydraulic interconnection between distinct sections of a studied groundwater system. A single analysis of dissolved ions is not helpful either. However, repeated measurements may indicate such mixing cases, as is further discussed in section 6.6. The very fact that the same spring or well reveals different ion concentrations at different times indicates several (at least two) water types are intermixing in a ratio that varies seasonally, or as a response to abstraction. Thus, the geological and hydrological models have to be modied to allow for an interconnection between distinct sections of the studied system. The topic is further discussed in section 6.6.


Chapter 3

3.7.4 Water Composition as a Tool to Identify Types of Rocks Existing in a Studied Groundwater System
The domain of groundwater is concealed, and we have only a limited number of glimpses at the geology, for example, at outcrops, and some information that is retrievable from drillings. As a result, it is hard to portray with certainty the lithology along the ow path. Complementary information is supplied by the chemical composition of groundwater: very fresh water reects contact with noncemented sandstone, basalt, or granite (section 3.1); water with a signicant concentration of calcium and HCO3 indicates passage through limestone; magnesium along with calcium and HCO3 indicates passage through dolomite; high SO4 concentration (greater than 2000 mg/l) indicates contact with gypsum; and high sodium and chlorine concentration (greater than 180,000 mg/l) reects contact with rock salt (section 3.1).

3.7.5 Composition of Stable Hydrogen and Oxygen Isotopes as a Tool to Distinguish Between Ongoing Recharge and Fossil Recharge
The composition of the stable hydrogen and oxygen isotopes of groundwater is controlled by the prevailing climatic and hydrological conditions (section 1.2), among other factors. Old groundwater that had been recharged under different climatic conditions is often distinguished by an isotopic composition that differs from the presently recharged groundwater (section 9.9). The Earth is at present in a relatively warm climatic phase, which means that the paleoclimates were mostly colder, in good correlation with published case studies that in general reveal that old groundwaters have relatively light isotopic compositions. Geological and hydraulic data leave open the question of whether a given groundwater system is a renewed resource, with ongoing recharge, or a nonrenewed resource, representing fossil recharge. In many instances the stable isotopes of the water provide the answer.

3.7.6 Composition of Water in Adjacent Wells as a Tool for Spatial Mapping of Stagnant Aquifers
Geological models are commonly portrayed in stratigraphic units (formations, members, epochs, etc.). These units often have large-scale extensions, leaving the hydrologist with the question of whether a studied setup consists of a single through-ow system or is made of numerous stagnant systems. The problem is especially acute in artesian wells situated in subsidence

Geological Data


structures (section 3.4). Adjacent wells with similar water composition are likely to belong to the same stagnant aquifer, whereas wells with signicantly different water compositions belong to different systems, stacked one upon the other or laterally adjacent. Thus ionic and isotopic compositions and concentration of age indicators supply the means to map the spatial distribution and extension of stagnant aquifers, helping to rene the geological and hydrological models.

3.8 Summary Exercises

Exercise 3.1: High-quality drinking water contains dissolved solids (a) below 800 mg/l, (b) above 2000 mg/l, (c) the more, the better. Exercise 3.2: Match the rocks on the left side with the (likely) properties on the right side: 1. Granite 2. Dolomite 3. Basalt 4. 5. 6. 7. Limestone Clay Chalk Marl A. Fractured B. Rich in interconnected pores and ssures C. Poor in interconnected pores and ssures D. Hosting good potable water E. Salinizing water F. Forming good aquifers G. Forming medium to poor aquifers H. Forming good aquicludes

8. Sandstone 9. Conglomerate Example Answer: 1A, D, and G.

Exercise 3.3: List rock properties that should be noticed and described in the eld work, relevant to hydrological and hydrochemical studies. Exercise 3.4: Study the location of the wells in Figs. 4.13a and b. How can water properties indicate whether wells I and II are interconnected and that wells III and IV are disconnected? Exercise 3.5: A water issuing in a spring contains 55 mg Cl/l. What is the likely source of this Cl?


4.1 Water Table Measurements

The depth of the water table in a well is measured relative to an agreed-upon mark at the top, for example, the edge of the casing. This reference point should be clearly marked to ensure reproducibility of the measurements. The depth of the water table is obtained in meters below the top of the well or, more meaningfully, in meters below the surface, as shown in Fig. 4.1. AC is the depth of the water table below the reference mark at the edge of the well casing (or any other selected mark). This might differ slightly from BC, the depth of the water table below the surface (Fig. 4.1). In the eld notebook the depth AC should be used, as it is exact and properly dened. In a nal report reference to the surface may be preferred. In any case, one has to specify how the depth is expressed: below well head or below surface. A variety of simple, accurate, and professional tools are available to measure water table depths to an accuracy of 0.2 cm. These instruments consist of a wire with a metal tip that is lowered and upon hitting the water an electrical circuit closes, indicating the water table (Fig. 4.2). The wire is marked for depth readings. The described mode of water table measurement can be performed only in an open, unequipped well. A pumped well can be specially equipped for water table measurements, and this is of interest as it reveals the local dynamics of the lowering of the water table due to abstraction (section 4.6). Regional interpretation of water table data obtained in many wells is done in meters above sea level (masl). Each well head has to be surveyed,

Physical Parameters


Fig. 4.1 Depth of water table: AC is the depth below the reference mark at the edge of the casing; BC is the depth below the surface.

and its altitude has to be determined. The measured water table depth is subtracted from the well head altitude in order to obtain the water table in absolute altitude units (Fig. 4.3).

Fig. 4.2 Depth of water table (WT) measurement, based on the closing of an electrical circuit, by the water: (a) one wire, the casing serving as the second wire (provided it is made of metal and unbroken); (b) two wires lowered into the well.


Chapter 4

Fig. 4.3 Expressing water table in altitude units (relative to sea level). The measured depth AB is subtracted from the altitude of point A, determined by direct measurement or read from topographic map. In the example, the reference point A has been determined to be 622 masl and the depth of the water table is 22 m. Hence, the water table in this well is 622 22 600 masl.

4.2 Interpretation of Water Table Data

The depth of the water table is of interest in the management of the well and helps in identifying the aquifer rocks. The water table altitude is needed for comparison of water tables in neighboring wells to determine the direction of water ow. Data may be processed as water table maps or as transects. These modes relate to a singular point in time, that is, the regional water table as measured at a certain date. The next stage of interpretation deals with time variations of the water table, often referred to as water table uctuations. The processing of water table measurements is herein dealt with in some detail as it is an integral part of the processing of hydrochemical and isotopic data.

4.2.1 Water Table Maps

Water table maps consist of equipotential linescontours of equal water table altitudes. The contours are drawn to t measured water table altitudes, as shown in Fig. 4.4. An immediate outcome is the deduction of the dominant direction of groundwater ow (Fig. 4.4b). A certain degree of ambiguity or subjectivity is inherent in the compilation of water table data. The solutions are not unique. Yet, in most cases, the general picture is clear. The ambiguities are reduced as the number of measured wells increases.

Physical Parameters


Fig. 4.4 Drawing equipotential lines: (a) a map with well locations and water tables in masl; (b) equipotential lines based on the well data; the arrows show deduced main directions of groundwater ow.

4.2.2 Water Table Transects

Water table transects portray the surface altitudes (topography) and water table altitudes of wells located along a line as shown in Fig. 4.5c. The transect provides a convenient picture of the local topography, depth of groundwater, spacing of existing wells, and inferred direction of groundwater ow. A water table transect may be superimposed on a geological transect, providing insight into the groundwater system, as shown in Fig. 4.6.

4.2.3 Water Table Fluctuations

The water table is dynamic in most systems. It changes in response to rain events, ood events, snowmelt, recharge, and pumping. To decipher the interplay of these ongoing processes, periodic water table measurements are essential. Historical data are in many cases available from local water authorities, which conduct routine water table measurements. Measurement of the depth of the water table at the time of each sample collection is essential in order to couple the chemical and isotopic results with the hydrological data. Repeated water table measurements in a well may be presented on a hydrograph, as a function of time. In the example given in Fig. 4.7, the low water table may be interpreted as reecting lack of recharge in the winter, and the rise may reect snowmelt recharge followed by summer rains. Countless combinations of hydrograph shapes and modes of interpretation are possible. Knowledge of local precipitation and climate is needed for proper interpretation. Rapid response to rain or ood events may indicate


Chapter 4

Fig. 4.5 Water table transect: (a) data table; (b) well location; (c) the transect, drawn through the numbered wells (x), having a NW-SE direction (o other wells, not included in the transect).

conduit-dominated intake, whereas response delayed by weeks or months indicates recharge through homogeneous porous media. Water table uctuations are occasionally accompanied by measurable variations in water temperature or composition, providing crucial information on mixing of different water types. Water table measurements are an important tool in tracing recharge. Three cases, reported by Winslow et al. (1965) are discussed in the following sections.

Physical Parameters


Fig. 4.6 Geological cross-section: (a) data abstracted from geological reports based on drill cuttings; (b) geological section (interpretation), along with the topographic (surface) and water table transects of Fig. 4.5.

Fig. 4.7 A hydrograph based on repeated measurements of the water table in an observation well. Possible interpretation: winter months reect restricted recharge, whereas starting in May snowmelt contributions are noticed, followed by summer rains.


Chapter 4

Fig. 4.8 Hydrograph of an observation well at the Saratoga National Historic Park, New York (after Winslow et al., 1965), and local precipitation graph. Interpretation is discussed in the text.

4.2.4 Recharge by Different Types of Precipitation

A detailed hydrograph, based on frequent water table measurements at an observation well at the Saratoga National Historic Park, New York, is given in Fig. 4.8, along with the local precipitation (Winslow et al., 1965). The authors offered the following interpretation: 1. Between January and May snowmelt provided some recharge, resulting in a slow rise of the water table. 2. In April began the rainy season, augmenting the continuing snowmelt, causing a water table rise. 3. In June began the principal growing season, causing increased transpiration losses that lowered the water table. 4. In September 4.7 inches of rain fell during a 4-day hurricane, and the water table rose slightly. 5. During the cold month of December only snow fell and the water table continued to decline.

Physical Parameters


This detailed tracing of recharge history, reected in the water table uctuations, is unique in its completeness and reects direct local recharge and the lack of pumping in the Saratoga Historic Park terrain. This case study demonstrates how rewarding a simple set of data can be, a topic to be further discussed in section 7.6 in relation to time-data series.

4.2.5 Recharge by a River

Recharge of a well by the Mohawk River, New York, has been demonstrated by Winslow et al. (1965) by studying hydrographs of the well and the river (Fig. 4.9): 1. The water table of the well followed the river during August. 2. In September a sudden rise in the river was caused by a ood event, followed by an immediate rise of the water table in the well. 3. Lowering the river level by the opening of the dam at the end of the navigation season (March) was followed by a sharp decline in the well. 4. A ood at the end of February caused a sharp rise in the well. 5. Stabilization of the river level at the beginning of the new navigation season was followed by a parallel stabilization in the well. The close response of the well to uctuations in the river level demonstrates that the well is dominantly recharged by the Mohawk River. Possible interference by pumping of adjacent wells may be ruled out on the basis of the monotonous abstraction, shown at the bottom of Fig 4.9.

4.2.6 Velocity of a Recharge Pulse

Changes in the water table of the Mohawk River and a number of adjacent observation wells is reported in Fig. 4.10, adapted from Winslow et al. (1965). The wells followed the river, with a time lag of 412 hours (insert in Fig. 4.10). Two possible explanations for this time lag may be envisaged: (1) arrival of the hydraulic pulse, or (2) arrival of the recharge front (assuming piston ow; section 2.1). To tell the two apart, the time lag observed for these wells by temperature measurements is helpful, as discussed in section 4.8 (see Fig. 4.21). The temperature time lag of, for example, well 58, has been observed to be about 3 months, whereas the water table time lag was only 12 hours. The latter denes the arrival of the hydraulic pulse, whereas the former denes the travel time of the recharge front. The distances given in the insert in Fig. 4.10, divided by the respective time lags, provided the


Chapter 4

Fig. 4.9 Hydrograph of the Mohawk River and water table variations in an adjacent observation well (following Winslow et al., 1965). The perfect match (text) proves recharge from the river. Pumping from adjacent wells (bottom) was steady and could not cause the observed changes of the water table in the well.

propagation velocity of the hydraulic pulse, which was 300 + 50 ft/h, or 100 + 20 m/h. The case studies discussed above, and depicted in Figs. 4.84.10, reveal the importance of repeated measurements, providing evolution with time, and the importance of auxiliary data, such as distribution of local precipitation or discharge in adjacent pumping wells.

4.3 Gradient and Flow Direction

The gradient, or drop in elevation, of the water along its path is a major factor in dening the water ow velocity, as dened by Darcys law (section

Physical Parameters


Fig. 4.10 Water table uctuations measured at wells near the Mohawk River (from Winslow et al., 1965). The wells followed a ood event with a time lag of several hours correlated with the distance from the river (insert table). The distance divided by the time lag provided the propagation velocity of the hydraulic pulse.

2.10). The gradient is expressed in meters drop of height per kilometer of horizontal ow trajectory, as shown in Fig. 4.11. The drop in water table levels between adjacent wells is computed from their water table data, and the distance between the wells is commonly read from a map on which the wells have been accurately marked. The gradient may also be extracted from a water table map by reading the drop in water table altitude between selected points, as shown in Fig. 4.12. Water ows mainly along the maximum gradient, as shown in Fig. 4.4b.

4.4 The Need for Complementing Data to Check Deduced Gradients and Flow Directions
Determination of the ow gradient between two wells (Fig. 4.11) is based on the assumption that the two wells are hydraulically interconnected, as shown in Fig. 4.13a. However, wells may be separated by an impermeable rock bed with no hydraulic interconnection (Fig. 4.13b). Thus the gradient measurement between the two wells in the second case is meaningless. The


Chapter 4

Fig. 4.11 Determining ow gradient. The drop of water table between wells I and II is Dh 412.6 411.8 0.8 m; the distance (read from a map) is 0.76 km. Hence the hydraulic gradient is 0.8 m/0.76 km 1.0 m/km.

same holds true for deduced directions of water owthey are meaningful provided the involved wells are hydraulically interconnected. Water ows from I to II in Fig. 4.13a, but it does not ow from III to IV in Fig. 4.13b. Geological information of the rock sequence and tectonic settings may be instructive but not denitive, as it is hard to translate eld data into hydraulic conductivity values: a shale bed may be fractured and let water ow through in one case, and a clay bed may be weathered and act as an aquiclude in another. In addition, a variety of processes lower the local water conductance, occasionally preventing lateral ow. An example of such a process is chemical clogging (Goldenberg et al., 1983). Other parameters are needed to check for hydraulic interconnections between studied wells. Chemical constituents of the water may indicate

Fig. 4.12 Extracting ow gradients from a water table map (contours in masl). Dh, from B to A, is 300.0 m 298.0 m 2.0 m, and the distance (read from the map) is 3.7 km. Hence the gradient between B and A is 0.54 m/km. The gradient from B to C is 0 m/km.

Physical Parameters


Fig. 4.13 Hydraulic interconnection between wells in ssured limestone terrain: (a) wells I and II are interconnected and water ows down-gradient; (b) similar-looking wells, separated by an impermeable rock bed; wells III and IV are not interconnected, in spite of the apparent gradient.

whether studied wells tap the same water type or belong to distinct water groups. In the latter case, hydraulic interconnections can be ruled out (section 6.5). The temperature of groundwater commonly increases downow, and hence if colder water is encountered along a suggested ow path, straightforward interconnection between wells is disproved (section 4.8). The isotopic composition of water provides additional clues to hydraulic interconnections (sections 9.10 and 9.11) and so do the radioactive age indicators tritium (section 10.7) and 14C (section 11.9).

4.5 Velocities and Pumping Tests

As stated in section 2.10, the velocity by which groundwater ows is commonly calculated from the water table gradient and the coefcient of permeability (k, or the related parameter of transmissivity). The k value is determined by a pumping test. During such a test a studied well is intensively pumped and the water table is monitored in it as well as in available adjacent observation wells. The change in water table level as a function of the pumping rate serves to compute the aquifer permeability. Pumping tests call for expertise that is beyond the scope of this book, but as shown in the next section the incorporation of hydrochemical methods is essential for safe interpretation of pumping test data.


Chapter 4

4.6 Chemical and Physical Measurements During Pumping Tests

The common interpretation of pumping test data is based on the assumption that only one aquifer is pumped and tested. However, the intensive pumping during the test causes a signicant local pressure drop in the pumped aquifer that may cause water from an adjacent aquifer to breach in (Fig. 4.14). If the pumping test is done in a phreatic aquifer, water of a lower conned aquifer may ow in. Similarly, in pumping tests in conned aquifers, an overlying phreatic aquifer may be drawn in. The breaching in of water from a second aquifer has to be detected so it can be included in the pumping test interpretation. Otherwise, the conclusions based on the test will be erroneous: apparent conductivities that are too large may be deduced, and exaggerated operation pumping rates may be suggested. To obtain the necessary information on the number of aquifers effectively included in a pumping test, continuous measurements of temperature, conductivity, and other parameters are recommended before, during, and after the test. Temperature is sensitive to aquifer depth (section 4.7) and is most useful in distinguishing different water systems (section 4.8). A constant temperature value, as shown in Fig. 4.15a, is a favorable indication that the pumping test remained restricted to a single aquifer. In contrast, in the example given in Fig. 4.15b, warmer water intruded into the pumped aquifer, and the latter part of the pumping test included water from two aquifers.

Fig. 4.14 Possible effect of a pumping test. The water table of aquifer I is drawn down near the well, a feature called a depression cone. Occasionally water from a lower conned aquifer may breach in (arrows across the aquiclude).

Physical Parameters


Fig. 4.15 Temperature measurements during pumping tests, expressed as a function of time and cumulative discharge: (a) temperature remained constant, indicating pumping remained constricted to a single aquifer; (b) temperature suddenly increased, indicating water from a warmer (probably lower) aquifer breached in.

Electrical conductivity is readily measured in the eld and reects the total amount of salts dissolved in the water (section 8.4). It is highly recommended that electrical conductivity be measured in short intervals throughout a pumping test. The data can be plotted against time or, preferably, against cumulative abstraction (Fig. 4.16). In the example it is seen that the intruding water is saltier. This result may be of importance for the regular pumping rate to be decided for the well. If the additional salinity is not harmful, then a relatively high abstraction rate may be recommended.

Fig. 4.16 Conductivity measurements during a pumping test: saltier water intruded in the pumped system after 12 hours, during which 3000 m3 were pumped.


Chapter 4

But if the additional salinity is unacceptable, then a low rate of routine abstraction has to be adapted. In these types of considerations the presentation of measured parameters as a function of both time and cumulative discharge is most useful. In the example of Fig. 4.16 the salty water broke through after pumpage of 3000 m3 in 12 hours. Hence, the routine pumping rate should be signicantly lower if only fresh water is wanted, and abstraction may be closer to the break-through value if water quantity is of prime importance and the quality of the mixed waters is acceptable. In addition to direct measurements, water samples should be collected for detailed chemical and isotopic analysis. As a rule of thumb, a pumping test should be accompanied by one sample taken before the test, representing the nondisturbed water system, and 10 samples collected periodically during the test. It is then suggested that the rst and last samples be fully analyzed. If they come out alike, and no temperature and electrical conductivity changes have been noticed, then one may condently conclude that the pumping test affected only one aquifer. If the rst and last samples differ from each other, then the rest of the collected samples should be analyzed to dene the nature and mixing percentages of the waters involved. Laboratory analyses are costly, but the information derived is of prime importance. Failure to notice the intrusion of a second water type may turn out to be a failure to predict possible deterioration of water quality in an overpumped well system. A case study of a documented pumping test is shown in Fig. 4.17, taken from a study in the Aravaipa Valley, Arizona. The outcome of a fully documented pumping test is a cornerstone of the hydrochemists report (section 18.2.5).

4.7 Temperature Measurements 4.7.1 Temperature Field Measurements

Commercial thermometers are adequate for most hydrological studies, their readings being good to +0.5 8C. However, they should be calibrated in the laboratory, as they are often off by about 1 8C. Calibration may be done by reading the thermometer in a fresh waterice mixture, providing 0 8C, and in boiling water, providing the local boiling temperature (determined by the local altitude). Needed corrections should be written on the instrument and applied to the eld readings. It is recommended that you always use two thermometers, as a check and as a spare in case of breakage. Temperatures should be read while the thermometer is dipped in the water, because upon removal the reading will drop rapidly while drying. If

Physical Parameters


Fig. 4.17 Tritium and 14C measurements during a pumping test conducted in a conned aquifer at the Aravaipa Valley, Arizona (Adar, 1984). Recent water of high tritium and 14C concentrations intruded from the overlying phreatic aquifer.

reading while dipped in the water is not feasible, a bottle should be lled with the water and the thermometer dipped in it. The temperature of the water of a spring should be measured as deep as possible. If the water pool of a spring is large, several readings should be taken to reach the extreme valuewarmest or coldestmost different from ambient air temperature. If the temperature measured at a spring is close to the ambient air temperature, temperature reequilibration of the near-surface spring water could have happened. A second measurement, at night or at a different season, may clear this point. If the same value is repeated, in spite of a variation in the ambient air temperature, then the measured spring temperature is the true one, reecting the temperature at depth.

4.7.2 Depth of Groundwater Circulation Deduced from Temperature Data

Temperatures measured in wells and mines reveal a general increase with depth, or a geothermal gradient (Fig. 4.18). The value of the geothermal gradient varies from one location to another, an average value being 3 8C/ 100 m. Groundwater is commonly temperature-equilibrated with the aquifer rocks. Temperatures measured in springs or wells reect the temperature attained at depth, and therefore provide information on the depth of


Chapter 4

Fig. 4.18 Temperature measurements in 48 deep wells in south Louisiana (from Bebout and Guttierrez, 1981). A gradient of 1.8 8F/100 ft, or 3 8C/100 m, is observed.

circulation. The calculation is straightforward: depthm T measured Tsurface DT/100

where Tmeasured is the measured spring or well temperature, Tsurface is the local average annual surface temperature obtained from climatological maps or local meteorological institutes, and DT is the local geothermal heat gradient established by geophysical studies. Example: A spring of 62 8C emerges in a region with an average annual surface temperature of 22 8C. The local heat gradient has not been measured, hence the value of 3 8C/100 m may be applied. The depth of circulation is 62 22 1330 m 3=100 Such values are minimum depth values, as the water may cool during ascent. This effect is smaller the larger the water ux is. Calculations reveal that in a spring or well with a discharge of 30 m3/h or more, cooling is negligible. For cases of lower discharge the calculated circulation depths are to be regarded as minimum values.

Physical Parameters


Temperature is the best and most reliable tool to establish the depth of groundwater circulation. Knowledge of the depth of circulation may be used to infer the types of rocks in the geological column and the area of recharge, topics to be discussed later on in light of case studies.

4.7.3 Type of Groundwater Flow Traced by Water Temperature Measurements

Recharge water often has a temperature that differs signicantly from the aquifer temperature. Continuous temperature measurements may thus serve as excellent recharge indicators. Fig. 4.19 shows biweekly temperature measurements, conducted by Shuster and White (1971) in springs of two regions of carbonate rocks in the central Appalachians. The researchers recognized, by independent observations, two types of springs: . . A conduit type of rapid karstic ow, recognized by adjacent sinkholes and by the muddy, or turbid, water A diffuse type, with slow ow through minute fractures in the rock, recognized by their clear water and lack of adjacent karstic morphology

The temperature records in Fig. 4.19 correlate well with this classication. The conduit type revealed signicant temperature variations, in good agreement with the known seasonal variations of karstic ow, whereas the springs with the diffuse type of ow revealed steady temperatures. Once the temperature pattern was established by calibration against other observa-

Fig. 4.19 Seasonal temperature observations in springs of the Penns Creek basin, central Appalachians (from Shuster and White, 1971). The authors classied the springs (text) into a conduit type with rapid karstic ow, and a diffuse type with slow ow through minute rock fractures. The former revealed signicant seasonal temperature variations, whereas the latter manifested a steady temperature.


Chapter 4

tions, the tool could be applied to the Paradise Spring (Fig. 4.19), dening it as a conduit type although no supporting eld data were available.

4.7.4 Mixing of Groundwaters

Mixing of different water types may occasionally be detected by temperature measurements, as, for example, a drop of temperature caused by the arrival of snowmelt recharge seasonally added to a regional base ow. Temperature measurements are most useful for detecting intermixing, especially when coupled with chemical and isotopic measurements, a topic discussed in sections 6.6 and 6.7.

4.8 Tracing Groundwater by TemperatureA Few Case Studies: The Mohawk River
A large-scale temperature study was reported by Winslow et al. (1965), studying recharge from the Mohawk River into gravel deposits underlying the river oodplain. They monitored temperatures in well elds with a total yield of 7 6 104 m3/day. The temperature data tracing the river recharge has been worked out in a number of modes, all providing superb examples for processing temperature data.

4.8.1 Contours of Equal Temperature Indicating Recharge from a River

Temperature data are occasionally presented in contours of equal groundwater temperature (results of measurements in a large number of wells). Contour maps are shown in Fig. 4.20 for 12 successive months during 1960 1961. The river temperatures (written in the lower left corner of each monthly map) are seen to decrease from 64 8F in the autumn to 32 8F (freezing) in the winter, and they warm to reach 77 8F in the summer. Thus, twice a year the temperature gradient between the river and the aquifer is reversed. The temperatures in the aquifer are seen to respond to these changes, but with a certain time lag. In October the temperature in the aquifer is about 75 8F near the river and 50 8F 900 m south, as compared to 64 8F in the river. This range drops to a minimum of 40 8F near the river and 50 8F 900 m away. By that time the river has already started to warm up. The aquifer reaches maximal temperatures of 75 8F near the river and 50 8F 900 m away in September, when the river is 77 8F. Give another glance to the October map to close the cycle. These signicant variations in the aquifer temperature, lagging behind the changes in the river, prove that the aquifer is recharged by the river. The changes are greater near the river (3575 8F)

Physical Parameters


Fig. 4.20 Monthly maps of equal groundwater temperature for a well eld bordering the Mohawk River (after Winslow et al., 1965). The river temperature changed over an annual cycle from 77 to 32 8F. The aquifer followed these temperature changes, indicating recharge from the river.

and are dampened away from it, until at a distance of 900 m to the south the temperature is steady (50 8F) year-round. This lateral temperature gradient points again to recharge from the river.


Chapter 4

4.8.2 Seasonally Repeated Depth Proles in a Well Indicating a Horizon of Preferred Flow
A second way of presenting the data of the temperature survey at the Mohawk River is in the form of seasonally repeated depth proles in a well (Fig. 4.21). The temperatures are seen to increase for half a year and then decrease, proving recharge, similar to the mode seen in the temperature maps (Fig. 4.20). The proles show the vertical dimension of the recharge temperature uctuations are accentuated between 180 and 200 ft. Recharge is most efcient in this horizon, indicating highest conductance.

4.8.3 Map of Contours of the Annual Range of Temperature Variations Indicating a Zone of Preferred Flow
Winslow et al. (1965) also expressed the results of their temperature study as a map of contours of the annual range of temperature variations (Fig. 4.22). The recharge from the river and the movement southward are seen in the

Fig. 4.21 Seasonal temperature proles in well 61, 100 m away from the Mohawk River (from Winslow et al., 1965). The temperatures are seen to decrease from OctoberMarch and to increase from JuneSeptember, similar to the trends seen in the temperature maps of the previous gure. The proles reveal that the largest temperature variations occurred at a depth interval of 180200 ft above sea level, indicating recharge occurred mainly through this part of the rock section, which in turn must have a higher conductivity.

Physical Parameters


southward damping of the range of annual temperature variations. A detail clearly born out is that of a zone of preferred conductivity, marked A in Fig. 4.22.

4.8.4 Temperature Time-Data Series Indicating Effective Flow Velocities

A fourth way in which temperature data from the Mohawk River were processed is shown in Fig. 4.23. Temperature observations over a whole year are plotted for six wells and for the river. Wells 54 and 59 are seen to follow

Fig. 4.22 Location map of wells near the Mohawk River with annual groundwater temperatures (from Winslow et al., 1965). Using these values, contours of equal annual temperature variation were drawn. The decrease of these contour values indicates water moves from the river into the aquifer, especially through the zone marked A.


Chapter 4

the pattern of the river, but with a time shift of about 2 months. Well 21, in contrast, reveals no resemblance to the river at all, and the rest of the wells have intermediate patterns. The degree of similarity to the river is correlated with the distance of the well from the river or, as more precisely stated by the researchers, the degree of similarity reects the hydraulic distance. By this they mean the combined effect of distance, conductivity, amount of water in transit, and temperature equilibration with the aquifer materials. The temperature graphs in Fig. 4.23 serve not only to demonstrate recharge, but the time lags in the response of each well to the temperature changes in the river may be divided by the distances from the river to provide effective water velocities. A treatment of this kind for all wells showed a zone of high velocities, marked A in Fig. 4.22.

Fig. 4.23 Temperature records over a whole year in wells near the Mohawk River (following Winslow et al., 1965). Wells 54 and 58 follow the river temperature changes with a time lag. Well 21, most distant from the river, revealed a steady temperature over the year, indicating that river recharge is probably not contributing to this well. The rest of the wells showed intermediate degrees of temperature response to the river temperature variations in proportion to their hydraulic distances.

Physical Parameters


4.9 Cold and Hot Groundwater Systems

Groundwater temperatures vary from a few degrees above freezing to boiling, and in geothermal wells steam at over 300 8C is produced. This high range of temperatures is caused by a variety of discharge mechanisms and, to a larger extent, by differences in the depth of circulation and local heat gradient values. Temperature data closely reect hydrological conditions, and several groups may accordingly be distinguished: . . . . Groundwater colder than local annual surface temperature occurs at high altitudes and is caused mainly by snowmelt recharge. Groundwater with a temperature close to the local average annual surface temperature belongs to the shallow active water cycle, circulation being limited to 100 m and, rarely, 200 m. Groundwater that is more than 6 8C above local average annual surface temperature circulates to appreciable depths, deducible from the heat gradient (section 4.7). Warm springs with temperatures up to 65 8C are common in tectonically bisected terrains, where groundwater can circulate to appreciable depths, or is stored in deep stagnant (trapped) aquifers. Most rift systems and active orogenic regions host hot springs that are explained in this way. Certain large synclines, or sedimentary basins, contain huge amounts of warm groundwater, exploitable for space heating. The Paris basin is an example. Geothermal systems host boiling springs and steam. Classical examples can be found in the United States (e.g., Yellowstone), Italy (e.g., Pisa), Iceland, New Zealand, and Japan. In the last decades methods of harvesting the energy of geothermal systems have been greatly advanced and a whole eld of geothermal prospecting and production has evolved. Geothermal manifestations are closely correlated to recent magmatic activity and movement of crustal plates. The associated waters are concentrated brines rich in CO2.

4.10 Discharge Measurements and Their Interpretative Value

Discharge is the measure of the amount (volume) of water emerging from a spring, or pumped from a well, per unit time. A wide array of discharge units exist in the literature, but cubic meters per hour (m3/h) is recommended. Discharge may, in certain cases, be measured in the eld


Chapter 4

with the aid of a container of known volume and a stopwatch. The discharge is calculated from the volume (number of times a vessel is lled) and the time involved. Occasionally spring water ows from several directions, the output is too large, or the well discharges into a closed system of pipes. In such cases the discharge information has to be obtained from the well operator or local water authority. Discharge of a spring or a well is a most informative parameter because it provides insight into the quantitative aspects of groundwater hydrology. Figure 4.24 includes monthly measurements of discharge, temperature, and chlorine content for a spring. Constant discharge is observed, indicating that water is delayed in the aerated zone, owing through a porous medium (in conduit-dominated recharge, seasonal recharge uctuations are reected in variations in spring discharge). In addition, constant discharge indicates that the water storage capacity of the system seems to be large compared to the annual recharge or discharge. The

Fig. 4.24 Monthly measurements of discharge, temperature, and chlorine concentration in a (hypothetical) spring. The three parameters are constant over the year, indicating only one type of water is involved, recharged through a porous medium (nonkarstic), and the systems storage capacity is large compared to the annual recharge and discharge.

Physical Parameters


accompanying temperature and chlorine values are also steady, indicating one type of water is involved in the system. Figure 4.24 shows two useful modes of presentation of recharge data: as a time series and as a function of other measured parameters. The conclusion that one type of water is involved can be deduced from the horizontal line in the time series diagram or from the narrow cluster of values in the parametric diagrams. Data plotted in Fig. 4.25 are from a different case, but resemble the parameters reported in Fig. 4.24. The obtained pattern is different: the discharge varied in an annual cycle, but the temperature and chlorine content remained constant; thus the interpretation is again of one type of water being involved, but recharge is via conduits of a karstic nature. Temperature is close to the average annual surface temperature, and uctuations in the recharge water temperature are damped by intermixing in the aquifer. Thus the storage capacity of the system is large as compared to the peak recharge. A third example, given in Fig. 4.26, reveals a case in which recharge varied seasonally in a spring, and temperature and chlorine content varied

Fig. 4.25 Monthly measurements of discharge, temperature, and chlorine in a spring. Temperature and chlorine are constant, revealing one type of water is involved. The signicant discharge variations indicate recharge is fast and of a karstic nature.


Chapter 4

as well, but in an opposite pattern (right diagrams in Fig. 4.26). The data plot along straight lines in the left diagrams of Fig. 4.26, revealing a negative correlation between recharge and temperature or chlorine content. Such correlation lines indicate intermixing of two water types, a topic fully addressed in section 6.6. A warmer and more saline type of water intermixes (in varying percentages) with a colder and less saline water. The highest possible temperature of the warmer end member might be deduced by extrapolation of the best-t line to zero discharge on the temperaturedischarge graph. A value of 20.3 8C is obtained. In a similar way, the highest possible value of chlorine concentration for the warm end member may be deduced by extrapolation to zero discharge in the chlorine-discharge diagram in Fig. 4.26. A value of 420 mg Cl/l is obtained. As zero discharge has no meaning in our context (a dry spring has no temperature or chlorine

Fig. 4.26 Monthly measurements in a spring. Discharge, temperature, and chlorine are seen to vary considerably, indicating more than one type of water is involved (e.g., base ow and seasonal additions) and recharge is karstic. The data plot along straight lines in the temperature-discharge and chlorine-discharge graphs, indicating two end members are intermixing in the spring system. The temperature and chlorine values of the warm and more saline end member may be deduced by extrapolation of the best-t lines to zero discharge (see text).

Physical Parameters


concentration), it is clear that the true intermixing water end members have values that lie between the extrapolated values (20.3 8C, 420 mg Cl/l) and the highest observed values (19 8C, 400 mg Cl/l). In this example the two sets of values are very close. The topic of water mixtures is discussed in sections 6.6 and 6.7. Discharge measurements often provide negative correlation lines, essential in nding end member properties. A case study from the Yverdon spring, western Switzerland (altitude 438 masl) is summarized in Fig. 4.27. Maxima in the discharge curve are seen in general to be accompanied by minima in the temperature and electrical conductivity (reecting salinity) curves, indicating a warm and more saline water intermixes with a colder and fresher water. The discharge and temperature data of the Yverdon spring have been replotted in Fig. 4.28. The best-t line, extrapolated to zero discharge, intersects the temperature axis at 30 8C. This is a maximum possible temperature of the warm end member in the Yverdon complex. The true end member temperature is between this extrapolated value (30 8C) and the highest observed temperature (24.3 8C).

Fig. 4.27 Discharge, temperature, and conductivity (reecting salinity) in a spring at Yverdon, western Switzerland (Vuatax, 1981). Temperature and conductivity varied in a negative correlation to discharge (Fig. 4.28), indicating mixture of two end members (see text).


Chapter 4

Fig. 4.28 Temperature-discharge data (from Fig. 4.27) of the Yverdon spring, western Switzerland. The negative correlation enables one to deduce an upper limit for the temperature of the warm end member (30 8C) by extrapolating to zero discharge (see text).

4.11 Summary Exercises

Exercise 4.1: Draw schematically a vertical section through a well and indicate (a) the casing and zone of perforation, (b) measuring reference point at the top of the well, and (c) the water table. Exercise 4.2: The altitude of a reference point of a well is 570 masl (what does this mean?) and the water table was measured to be at a depth of 27 m. What is the altitude of the water table (use the relevant units)? Exercise 4.3: Study Fig. 4.4. Do the arrows show the only direction of water ow? Exercise 4.4: Study Fig. 4.6. On what evidence has the fault been plotted? Could a different interpretation be offered?

Physical Parameters


Exercise 4.5: Is there a good correlation between local precipitation and water level in the case plotted in Fig. 4.8? Can you comment on this correlation? Exercise 4.6: Observe the high correlation and immediate responses between the river level and the water table in adjacent wells, shown in Figs. 4.9 and 4.10. What is the nature of water ow from the river to the wells? Exercise 4.7: Why, in the terms discussed above, is there no ow from well C to the direction of well B in Fig. 4.12? Exercise 4.8: Study Fig. 4.14. What may happen if aquifer II is strongly pumped? Exercise 4.9: Playing devils advocate, can you claim that the results in Fig. 4.15a (upper diagrams) do not exclude breaching-in of water from a second aquifer? Exercise 4.10: Fig. 4.20 is loaded with data. Do you understand the conclusion drawn? Try to go in steps: compare the given river temperature with the equal temperature line for the wells closest to the river in (1) October 1960, (2) January 1961, (3) March 1961, and (4) September 1961. What trend is seen? Exercise 4.11: The contours in Fig. 4.22 depict _____ (ll in). What is the general trend of these values as a function of distance from the river? What can be concluded? Exercise 4.12: The lines in Fig. 4.27 make a dramatic impression (check). However, one should also study the gures given on the axes. Doing so, are the changes in the parameters of the Yverdon spring really signicant?


~~~~~~~~ Measured Parameters and Observations

lead to

Boundary Conditions
that dene

Conceptual Models ~~~~~~~~


The outcome of hydrochemical studies is based on chemical data and their interpretation. A clear knowledge of basic terms, units applied, and the nature of analytical errors is essential to avoid confusion and mistakes. The following concepts and denitions have to be mastered as a prerequisite to data processing.

5.1 Elements
To dene an element one has to discuss the basic units of naturethe atoms. Atoms have a nucleus that consists of two main types of particles: protons, which have a positive charge, and neutrons, which are neutral. Around the nucleus orbit much smaller particles with a negative charge, called electrons. In each atom the number of orbiting electrons matches the number of protons in the nucleus, balancing the negative and positive charges and making the atom neutral. The chemical properties of atoms are dened by the number of electrons, which in turn are dened by the number of protons in the nucleus. Chemical elements consist of atoms of only one kind. Hydrogen atoms contain one proton, helium atoms contain two protons, oxygen atoms contain eight protons, and uranium atoms contain 92 protons (Table 5.1).


98 Table 5.1 Atomic Weights and Valences Element Hydrogen Helium Carbon Nitrogen Oxygen Sodium Magnesium Silicon Sulphur Chlorine Potassium Calcium Bromine Compound Bicarbonate Sulphate Nitrate Symbols H He C N O Na Mg Si S Cl K Ca Br Formula HCO 3 SO2 4 NO 3 Protons 1 2 6 7 8 11 12 14 16 17 14 20 35 Ionic weight 1 12 48 61 32 64 96 14 48 62 Atomic weight 1.0 4.0 12.0 14.0 16.0 23.0 24.3 28.0 32.0 35.5 39.1 40.0 80.0 Valency 1 2 1 Electrons 1 2 2,4 2,5 2,6 2,8,1 2,8,2 2,8,4 2,8,6 2,8,7 2,8,8,1 2,8,8,2 2,8,8,17

Chapter 5

Valency 1 0 4 3 to 5 2 1 2 4 2 to 6 1 1 2 1

5.2 Isotopes
The number of neutrons in an atomic nucleus either equals the number of protons or is slightly greater. Most elements have several types of atoms, differing in the number of neutrons that accompany the protons, whose number is xed for each element. For example, hydrogen atoms (one proton) are known with no neutron, with one neutron, and with two neutrons. Such varieties in the number of an elements neutrons are called isotopes (Greek isos, equal, and topos, place, referring to the place in the Periodic Table). Hydrogen thus has three isotopes, and they have been given special names and symbols: Hcommon hydrogen, 1 proton Ddeuterium, heavy stable hydrogen, 1 proton 1 neutron Ttritium, radioactive hydrogen, 1 proton 2 neutrons Another way to describe an isotope is to add the number of particles in the nucleus (protons neutrons). This number is placed at the upper left

Elements, Isotopes, Ions, Units, and Errors


corner of the symbol of the element. Thus the hydrogen isotopes may be written
1 2

Hcommon hydrogen, 1 proton Hdeuterium (also written D), 1 proton 1 neutron 3 Htritium (also written T), 1 proton 2 neutrons Carbon isotopes are Ccommon carbon, 6 protons 6 neutrons Cheavy stable carbon, 6 protons 7 neutrons 14 Cradiocarbon, 6 protons 8 neutrons
12 13

Oxygen Isotopes are Ocommon oxygen, 8 protons 8 neutrons Oheavy (very rare) oxygen, 8 protons 9 neutrons 18 Oheavy oxygen, 8 protons 10 neutrons
16 17

The relative amounts of the individual isotope species in each element, expressed in percent, are called the isotopic abundances. For example, in seawater the relative abundances of hydrogen isotopes are
1 2

H99.984% H (or D)0.016% 3 H (or T)approximately 5 6 106% and the isotope abundances of oxygen in seawater are
16 17

O99.76% O0.04% 18 O0.20% The isotopic abundances vary slightly in different natural materials. Tables have been compiled giving the average isotopic abundances as observed in terrestrial materials. Differences in isotopic compositions observed in groundwaters provide the basis for powerful tracing methods, discussed in Chapter 9.

5.3 Atomic Weight

The atoms of different elements and of their isotopes differ from each other in their masses or weights. By international convention common carbon (12C) has been dened as having an atomic weight of 12. On this basis common hydrogen (1H) has an atomic weight of 1, common oxygen (16O) has an atomic weight of 16, and 238U has an atomic weight of 238.


Chapter 5

Isotopes have specic atomic weights, according to their number of neutrons. Thus the atomic weight of 35Cl is 35, that of 37Cl is 37, and the average atomic mass of chlorine is in between, at 35.5. The average atomic weights of the elements have been determined from two sets of data: the atomic weight of each isotope and the relative abundances of those isotopes. From these data the weighted average atomic weight of each element has been calculated. Atomic weights for elements of hydrochemical interest are included in Table 5.1.

5.4 Ions and Valences

The arrangement of electrons orbiting around atomic nuclei obeys strict rules. As the number of electrons increases, from light atoms to heavy atoms, they are arranged in concentric orbits, constituting shells: Innermost shellup to 2 electrons Second shellup to 8 electrons Third shellup to 8 electrons Fourth shellup to 18 electrons Fifth shellup to 18 electrons In heavier elements the rules are slightly more complicated. Atoms with complete electron shells are chemically inert. Examples are the noble gases: He (2 electrons) Ne (10 electrons, 8 in the outer shell) Ar (18 electrons, in shells of 2, 8, and 8) Kr (36 electrons, in shells of 2, 8, 8, and 18) Xe (54 electrons, in shells of 2, 8, 8, 18, and 18) All other atoms tend to interact with each other by sharing the electrons in their outer shells. The interacting atoms thus achieve complete outer shells of 2, 8, or 18 electrons. For example, Na electron shells of 2; 8; 1 Cl 2; 8; 7 NaCl In this case sodium gives away its single outer electron, being left with its next complete shell of eight electrons. As a result, the sodium atom loses a negative charge and one of its protons is left nonbalanced. In other words, the sodium atom in the NaCl atom combination has one positive, nonbalanced, charge. Thus, it is no longer an atom, which is dened as neutral entity. The new product is called an ion and it is marked by a sign next to the chemical symbol: Na. Similarly, the chlorine atom in NaCl

Elements, Isotopes, Ions, Units, and Errors


gained an electron and completed an outer shell of eight electrons. Thus, the chlorine is now an ion too, but with a negative charge: Cl. Positively charged ions are called cations (so called because in electrolysis they move to the cathode) and negatively charged ions are called anions (traveling to the anode). Let us examine another example: Ca2 Cl Cl CaCl2 In this case each of the chlorine atoms received an electron and was turned into an anion, Cl. The calcium atom (20 electrons, arranged in shells of 2, 8, 8, and 2) donated its two outermost electrons, remaining with a complete outer shell of eight electrons. Thus a double-charged cation, Ca2, was formed. The number of electrons that an atom gives, or gains, is called its valency. In the examples so far discussed, Cl has one (negative) valency and Ca2 has a double (positive) valency. In other words, calcium is bivalent. Valences of selected elements are given in Table 5.1.

5.5 Ionic Compounds

Groups of atoms of certain elements combine in a rather stable state, making up ionic compounds. An example is CaCO3, the compositional formula of limestone, composed of Ca2 CO2 . A second example is 3 CaSO4, the compositional formula of anhydrite, composed of Ca2 SO2 . 4 In the above examples CO2 and SO2 are ionic compounds. Their 3 4 ionic weights are the algebraic sum of the atomic weights of the atoms involved: the ionic weight of CO2 is 12 (3 6 16) 60, and the ionic 3 weight of SO2 is 32 (4 6 16) 96. The valences of ionic compounds are 4 the algebraic sum of the valences of the atoms involved. Thus the valence of carbonate is C4 O2 O2 O2 CO2 3 and the valency of sulfate is S6 O2 O2 O2 O2 SO2 4 Ionic compounds commonly dissolved in groundwater include HCO 3 (bicarbonate), CO2 (carbonate), SO2 (sulfate), and NO (nitrate). 3 4 3

5.6 Concentration Units

The concentration of ions dissolved in water is expressed in a variety of ways:


Chapter 5

Weight per volume. The units most commonly used are milligram per liter (mg/l), for major ions, and microgram per liter (mg/l), for trace elements. For example, data for groundwater from the Uriya 3 well are given in Table 5.2 in weight per volume units. Weight per weight. These units are commonly applied to highly saline waters. Units in use include grams per kilogram (g/kg) and milligrams per kilogram (mg/kg). An example for the Dead Sea brines is given in Table 5.3. The conversion from weight per volume to weight per weight units is performed by dividing the former by the density of the brine, for example, 1.23 for the Dead Sea example in Table 5.3. Ionic equivalence units. The number of anions in solution always equals the number of dissolved cations. Interactions of aqueous solutions with rocks always end up in ionically balanced solutions. Thus for the discussion of chemical processes it is most meaningful to express chemical data in ionic equivalence units, or equivalents: 1 equivalent number of grams equal to ionic weight valence

For example, 1 equivalent of Na is 23/1 23 g, and 1 equivalent of SO2 is 4 96/2 48 g. The data needed to calculate the equivalents of common ions are given in Table 5.1. Equivalent units are too large for convenient use for common waters, and therefore the milliequivalent (meq) unit is used: 1 meq of Na 23 mg, and 1 meq of SO2 48 mg. Milliequivalent units are applied 4 per volume units, as in meq/l, or per weight units, as in meq/g.

5.7 Reproducibility, Accuracy, Resolution, and Limit of Detection

Data should be reported with a description of their quality. For example, the temperature of a spring measured by one person ve times in succession was 16.5, 17.2, 14.0, 15.7, and 16.98 C. The same spring measured by a second person ve times in succession yielded 16.0, 16.1, 15.8, 16.1, and 16.48 C. A quick glance reveals that the second persons measurements are closer to each other, or to use a more technical expression, the second set of data reveals a higher degree of reproducibility. This degree of reproducibility may be expressed quantitatively by calculating the mean deviation for the sets of data. The mean value in the rst set of temperature measurements is 16.18 C and the mean deviation is +1.08 C. Hence, the mean value of the rst set of measurements is 16.18 C + 1.08 C. The mean value of the second set of measurements is 16.18 C + 0.28 C. Hence, the reproducibility in the

Elements, Isotopes, Ions, Units, and Errors Table 5.2 Dissolved Ions, Uriya 4 Well, Israel (temperature 28.68 C, pH 7.05) mg/l (ppm) K Na Ca Mg Sr Cl SO4 HCO3 Si 7.0 253 84 35 1.9 405 74 354 7 mg/l (ppb) 5 510 90 <0.2 4 3 34 32 5 100 18.3 18.7 37.0 1.1% meq/l 0.18 11.0 4.2 2.9 11.4 1.5 5.8


Al B Br Cl Cr Co Fe Mn Ni P Total cations Total anions Total dissolved ions (TDI) Reaction error

Source: Arad et al. (1984) and Kroitoru (1987). Estimated analytical errors: +5% for major ions; 1015% for minor ions.

Table 5.3 Chemical Composition of Dead Sea Brines (March 1977, density 1.23 g/ cm3) K g/l g/kg 7.65 6.22 Na 40.1 32.6 Ca2 17.2 14.0 Mg2 44.0 35.8 Br 5.3 4.3 Cl 225 183 SO42 0.45 0.37 TDI 340 276

Source: Kroitoru (1987).


Chapter 5

second set was better and the data of that set were of higher quality. Reproducibility may be best expressed in percentages; for example, the reproducibility of the rst persons temperature measurements was 1.0 6 100/16.1 +6.2%, whereas the second persons reproducibility was +1.2%. A second property of data quality is their agreement with standard measures. For example, is a thermometer used in the eld calibrated by comparison to a standard thermometer? Does it show 08 C in a bath of ice and distilled water, and does it show precisely the local boiling temperature? The agreement with standard measures is called accuracy. A good thermometer has an accuracy of +0.28 C, but many commercial thermometers have lower accuracies, as they may be off a calibrated instrument by 1.08 C or more. Accuracy of chemical analytical data is tested by the analyst with solutions that are carefully prepared from chemically pure compounds. A third property of data quality relates to the resolution. Thermometers may be long or short. In the rst case readings in 0.28 C intervals are possible, whereas in the second case only 18 C intervals are readable. Thus, the resolution of the long thermometer is 0.28 C and that of the short is 1.08 C. Similarly, chemical laboratory data should be reported along with resolution, dened by the instruments involved. Knowledge of the resolution is needed to distinguish differences that are analytically signicant. For example, if chlorine is determined with a resolution of 0.5 mg/l, then values of 22.7 and 23.1 mg/l are nondistinguishable, whereas 22.5 and 25.8 mg/l reveal a difference that is more than twice the resolution and is therefore analytically signicant (this point is further discussed in section 5.8) A fourth property of signicance in data quality assessment is the limit of detection, that is, the lowest value detectable. This value has to be known in order to properly process very low concentration values. If the limit of detection for lithium is 0.015 mg/l, then a value of 0.07 mg/l is analytically signicant (this point is further discussed in section 5.8).

5.8 Errors and Signicant Figures

As seen in the previous section, measured values are not absolute, but are obtained with a certain degree of uncertainty. The uncertainty is caused by the combined effect of several error sources. Four major sources for data uncertainty were described in the previous section: reproducibility, accuracy, resolution, and limit of detection. To these may be added other factors: instability of instrumentation, contamination, accuracy in preparation of standard solutions, etc. The sum of all uncertainties is called the analytical error. The analytical error is a cumulative outcome of all errors

Elements, Isotopes, Ions, Units, and Errors


involved in a measurement. Data included in a laboratory report should always be accompanied by the relevant analytical error, written with a + sign to the right of the result; for example, 25.62 + 0.50 mg/l. The analytical error is occasionally expressed as a percentage of the obtained value. Thus, 25.62 + 0.50 mg/l may also be stated as 25.62 mg/l +2%. In certain cases the analytical error is not computed for each value, but is given in a general mode, for example, in the bottom line of a table, as follows: analytical errors: Na: +0.50 mg/l, Ca: +0.70 mg/l, etc.; or Na: +2%, Ca: +2.55, and so on. The analytical error is needed to decide which data differ from each other with analytical signicance: only data that differ by more than the relevant analytical error should be regarded as different for purposes of data processing. Accordingly, data should be reported only in signicant gures. SO2 concentrations of 16.273 mg/l or 106.16 mg/l are meaningless if the 4 analytical error is, for example, +0.7 mg/l. In such a case the data should be reported using only signicant gures, namely, 16.3 mg/l and 106.2 mg/l.

5.8.1 Reaction Error

The sum of cations equals the sum of anions in each solution. The deviation from such an equality provides another way to assess data quality. The equation used is Reaction error Scations Sanions 6100 Sions

The reaction error is thus expressed as a percentage of the total ion concentration. Positive reaction errors indicate cation excess; negative errors indicate anion excess. Reaction errors are caused by the analytical errors of the individual parameters and the fact that not all possible ions are commonly measured. In certain cases it is worthwhile to enlarge the list of ions analyzed in order to lower the reaction error, for example, to include NO , Fe3, or 3 PO4 . 4 At the beginning of each study a decision has to be made as to which reaction errors will be acceptable. A cutoff at 2 or 5% is common. Analyses with high reaction errors are omitted in the data processing and, if possible, they should be discussed with the laboratory personnel.

5.9 Checking the Laboratory

Only in rare cases do eld hydrochemists themselves measure all the parameters required. In most cases samples are sent to laboratories for part,


Chapter 5

or all, of the measurements. It is the hydrochemists duty to discuss data quality with the laboratory and obtain, at least, the analytical error and limit of detection for each parameter measured. In addition, laboratories should be checked by their clients. There are several kinds of laboratory checks.

5.9.1 Duplicate Samples

Each batch of samples sent to the lab should include duplicates of one sample, sent with different names and sample numbers. The results from the duplicate sample give a picture of the quality of the data. If the duplicates fall in the range of the quoted analytical error, the data for the whole batch of samples are acceptable. If, however, the duplicate values differ by more than the stated analytical error, the results should be discussed with the laboratory personnel and the data for the whole sample batch should be regarded as questionable. The differences observed between duplicate samples of several sample batches establish the analytical error of the specic laboratory for each parameter.

5.9.2 Dilution of a Sample

Samples should be diluted with measured amounts of distilled water. The results of the diluted sample are acceptable if they agree with the calculated diluted value within the stated analytical error. Example: A water sample has been diluted with 1 volume of distilled water. The laboratory results for magnesium were 105 mg/l for the nondiluted sample and 52.9 mg/l for the diluted sample; the analytical error was 0.8 mg/l. Thus the reported diluted value, 52.9 + 0.8 mg/l, included in its range the calculated value for a 1:1 diluted sample, 52.5 mg/l, and the magnesium data from the laboratory may be accepted for the whole batch.

5.9.3 Standard Water Sample

A highly recommended procedure is to collect a large sample of groundwater, keep it in a cold dark place (to avoid bacterial decomposition), and add a sample of it with every batch of samples sent to the laboratory. This provides a continuous check, revealing the analytical error and serving as a monitor of laboratory performance.

Elements, Isotopes, Ions, Units, and Errors


5.10 Evaluation of Data Quality by Data Processing Techniques

Awareness of data quality information is, unfortunately, limited. A large number of articles are published with no analytical errors or limits of detection, and the results are often stated using nonsignicant gures. A major source for hydrochemical data are archives containing valuable historical data (section 7.5). These, too, are often without quality descriptions. As a result, investigators tend to discard such data as nonreliable, in spite of their high potential value for describing early stages of local water exploration. Data processing methods provide a substitute for the missing description of analytical data. Repeated measurements of the same water source are occasionally available. In such cases a mean value may be calculated for each parameter (dissolved ions, pH, or temperature). The standard deviations of these values serve as an estimate of the analytical error. In fact, these standard deviations also incorporate the natural uctuations in the measured water source. Therefore, these mean deviations serve as conservative estimates to the analytical errors. These estimated errors may then be applied to all the data reported from the same laboratory during the same period. Experience shows that old data are often good and acceptable.

5.10.1 Reproducibility Deduced from Clustering of Data

A basic step in the processing hydrochemical data is to plot the various parameters as a function of the total dissolved ions (TDI) or other parameters (sections 6.3 and 6.4). Occasionally a group of hydrologically related samples cluster, or group, around the same values (e.g., wells tapping the same aquifer). In such cases the mean deviation from the mean value, observed for each dissolved ion, serves as an upper limit for the analytical error (it also includes the natural uctuations).

5.10.2 Reproducibility Deduced from Data Plotting on a Mixing or Dilution Line

As discussed in section 6.6, data occasionally plot along a well-dened line (in most cases a mixing line). The mean deviation from such a line provides an upper limit for the sum of analytical errors for the parameters plotted.


Chapter 5

5.11 Putting Life into a Dry Table

Mastering the units and data quality concepts discussed in this chapter is absolutely necessary in order to proceed with the remaining chapters in this book, and to enjoy hydrochemistry. A new hydrochemical study, commenced in Wonderland, included the collection of ve identical sample bottles from the Wisdom Spring. They were transferred to a laboratory at different dates for determination of major dissolved ions; the data are given in Table 5.4. What can be deduced, or calculated, in light of the data quality concepts and data processing approaches discussed in the previous sections? Sending several bottles of the same water provides the data needed to calculate the laboratorys reproducibility (section 5.7). This procedure is recommended at the beginning of a hydrochemical study, when using a new laboratory, or as a periodic check of a known laboratory (section 5.9). From the data of Table 5.4 it can be seen that the chlorine value of sample 1 is signicantly higher than the chlorine values of the other four samples. An inquiry to the laboratory may reveal that it was a typographical error, and 43.2 should be corrected to 4.32. The mean sodium value is 4:52 4:93 5:24 4:92 4:67 4:856 5 or, in signicant gures, 4.86 meq/l.

Table 5.4 Dissolved Ions, Wisdom Spring, meq/l Sample No. 1 2 3 4 5 K 0.40 0.37 0.41 0.37 0.33 Na 4.52 4.93 5.24 4.92 4.67 Ca2 1.23 1.44 1.67 1.35 1.23 Mg2 0.91 0.97 1.03 1.09 0.95 Cl 43.2 4.75 5.11 5.01 4.82 HCO3 1.95 2.46 2.72 2.51 2.03 SO42 0.21 0.01 0.17 0.02 0.1

Perfect Analytics Laboratory, Chemistryland.

Elements, Isotopes, Ions, Units, and Errors


The deviation of each sodium measurement from the average is given below:
Sample 1 2 3 4 5 mean Na 4.52 4.93 5.24 4.92 4.67 4.86 Deviation 0.34 0.07 0.48 0.06 0.19 0.23

Thus the value of 4.52 reported for sodium in sample 1 deviates from the mean value by 4:86 4:52 0:34 meq=l A minus sign is needed to specify that measurement 1 was lower than the mean. The sum of negative deviations (in our example: 0.34 0.19 0.53) should be close to the sum of the positive deviations (0.07 0.48 0.06 0.61), indicating that the mean value (4.86) and the deviations have been correctly calculated. The two sums may differ slightly (0.53 versus 0.61) due to rounding up of each value to its signicant gures. The mean deviation is calculated from all deviations regardless of their positive or negative sign. In the present example, 0:34 0:07 0:48 0:06 0:19 0:228 5 or, in signicant gures, 0.23. The mean deviation of the sodium measurements reported in Table 5.4 is +0.23, and the mean sodium concentration is 4.86 + 0.23 meq/l. The mean deviation and the standard deviation (more familiar to some students) are numerically very close. They are often also called sigma (after the Greek letter). Data are commonly reported with one sigma (4.86 + 0.23 in our sodium example). Statistically, if additional measurements of the same type are done, 67% of the cases will fall in the one-sigma range, 90% of the cases will fall in the two-sigma range (4.86 + 0.46 in our Na example), and 97% of the cases will fall in the three-sigma range. By convention, results are reported with one sigma unless otherwise specied. Table 5.4 has been


Chapter 5

Table 5.5 Mean Concentrations (meq/l), Mean Deviations, and Reproducibilities for the Wisdom Spring Data (Table 5.4) Sample 1 2 3 4 5 K 0.40 0.37 0.41 0.37 0.33 Deviation 0.02 0.01 0.03 0.01 0.05 +0.03 +7.9% Na 4.52 4.93 5.24 4.92 4.67 4.86 Deviation Ca2 Deviation Mg2 Deviation 0.34 0.07 0.48 0.06 0.19 +0.23 +4.7% 1.23 1.44 1.67 1.35 1.23 1.38 0.15 0.06 0.29 0.03 0.15 +0.14 +10% 0.91 0.97 1.03 1.09 0.95 0.99 0.08 0.02 0.04 0.10 0.04 +0.06 +6.1%

Mean 0.38 Reproducibility Sample 1 2 3 4 5

Cl Deviation HCO3 Deviation SO42 Deviation 4.32 4.75 5.11 5.01 4.82 0.48 0.05 0.31 0.21 0.02 +0.21 +4.5% 1.95 2.46 2.72 2.51 2.03 2.33 0.38 0.13 0.39 0.18 0.30 +0.28 +12% 0.21 0.01 0.17 0.02 0.11 0.10 0.11 0.09 0.07 0.08 0.01 +0.07 +70%

Mean 4.80 Reproducibility

reworked in Table 5.5, which includes the average, or mean, concentrations of the various ions and the reproducibilities. The total concentration of dissolved cationstotal cationsis the sum of the concentrations of K, Na, Ca, and Mg: 0:40 4:52 1:23 0:91 7:06 meq=l The average total anions is 4:32 1:95 0:21 6:48 meq=l The value of total dissolved ions (TDI) is 7:06 6:48 13:54 meq=l The reaction error (section 5.8) is the difference between total cations and total anions, expressed as a percentage of the TDI. For sample 1 of Table 5.4 this would be 7:06 6:48 6100 4:3% 13:54

Elements, Isotopes, Ions, Units, and Errors


The data of Table 5.4 have been reworked again in Table 5.6, which includes the total cations, total anions, total ions, and reaction errors. The data in Table 5.4 have been expressed in meq/l. However, most people are used to the mg/l units for assessment of the degree of salinity of water. The conversion of meq/l data into mg/l was discussed in section 5.6, and is here demonstrated on the Wisdom Spring data (Table 5.7): Na : K : 4:52623:0 104 mg=l 1

0:40639:1 15:6 mg=l 1 1:23640:0 24:6 mg=l 2 0:91624:3 11:0 mg=l 2

Ca2 : Mg2 : Cl :

4:32635:5 153 mg=l 2 1:95661 119 mg=l 1

HCO : 3 SO2 : 4

0:21696 10:1 mg=l 2

Comparing the raw data in Table 5.4 with Tables 5.5, 5.6, and 5.7 and the relevant discussion, the reader may, perhaps, be amazed how much life can be put into a single table of dry data.

Table 5.6 Total Ions (meq/l) and Reaction Errors, Calculated for the Wisdom Spring Data (Table 5.4)
Sample 1 2 3 4 5 K 0.40 0.37 0.41 0.37 0.33 Total Total Total Reaction error Na CA2 Mg2 Cl HCO3 SO42 cations anions ions 4.52 4.93 5.24 4.92 4.67 1.23 1.44 1.67 1.35 1.23 0.91 0.97 1.03 1.09 0.95 4.32 4.75 5.11 5.01 4.82 1.95 2.46 2.72 2.51 2.03 0.21 0.01 0.17 0.02 0.11 7.06 7.71 8.35 7.73 7.18 6.48 7.22 8.00 7.54 6.96 13.54 14.93 16.35 15.27 14.14 4.3% 3.3% 2.1% 1.2% 1.6%

112 Table 5.7 Dissolved Ions in Samples of Wisdom Spring (mg/l) Sample 1 2 3 4 5 K 15.6 14.5 16.0 14.5 12.9 Na 104 113 120 113 107 Ca2 24.6 28.8 33.4 27.0 24.6 Mg2 11.0 11.8 12.5 13.2 11.5 Cl 153 169 181 178 171 HCO3 119 150 166 153 124

Chapter 5

SO42 10.1 0.5 8.2 1.0 5.3

TDI 428 >488 >537 >500 >456

5.12 Evaluation of Calculated Reproducibilities and Reaction Errors

Reproducibility of measurements of major dissolved ions can, in theory, be better than +1%. However, in real life poorer reproducibilities are common. In Table 5.5 the reproducibility values of +4.7% for the sodium data and +4.5% for the chlorine data are on the limit of acceptance. However, +10% for calcium and +12% for HCO3 are shaky, and the value of +70% for SO4 is totally unacceptable. In the Wisdom Spring example, the investigator should discuss the results with the laboratory staff and see whether they can improve. Otherwise, it will be necessary to shift to another laboratory and repeat the check. As stated, reaction errors are another way to estimate data quality (section 5.8). The reaction error can (and should) be better than 1%, but they are often larger. Many investigators will accept up to 5%. Using the latter criterion the reaction errors calculated in Table 5.6 (4.3%, 3.3%, 2.1%, 1.2%, and 1.6%) are acceptable. This example brings out a major shortcoming of the reaction error quality test: the poor reproducibility of the SO4 data, demonstrated above, is not reected in the reaction error because SO4 is a minor compound of the Wisdom Spring water. Low reaction errors indicate acceptable quality of the data for the major ions alone. The reaction errors in repeated measurements are expected to be random, that is, in part of the measurements the total cations will exceed the total anions and in the rest of the cases the total cations will exceed the total anions. However, occasionally a systematic pattern is seen. In Table 5.6 all the measurements reveal total cations to be higher than total anions (check it). Possible explanations are:

Elements, Isotopes, Ions, Units, and Errors


A systematic analytical error in one (or more) of the ions The list of measured anions should include other ions that happen to be important, for example, carbonate (CO2 ), nitrate (NO3), or bromide 3 (Br)

5.13 Summary Exercises

Exercise 5.1: Provide the following information for magnesium: atomic weight, valence, and how many mg/l there are in 1 meq/l of magnesium. Exercise 5.2: Match the symbols in the rst column with the items in the second column: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Ar HCO 3 16 O NO 3 SO2 4 Ca2 D Br 3 H 4 He A. Anion of sulfate. B. The light isotope of oxygen. C. Noble gas argon. D. Deuterium, a heavy isotope of oxygen. E. The element bromine. F. The bicarbonate anion. G. The heavy and common isotope of helium. H. The anion nitrate. I. Tritium, a radioactive hydrogen isotope. J. The bivalent cation of calcium.

Exercise 5.3: What is the unit meq/l? What is its denition? What is 1 meq/l of chloride? Exercise 5.4: What is the reaction error for the data of sample 73 of the Green Mice Spring reported in Table 6.2? Exercise 5.5: What is the reproducibility concept? Five bottles of water collected at the same time at a spring were sent to a laboratory and the following values were obtained for the potassium concentration: 12.2 mg/l, 11.9 mg/l, 11.9 mg/l, 12.1 mg/l, and 12.0 mg/l. What is the reproducibility? Exercise 5.6: The reported resolution of chlorine measurements at a certain laboratory is 2 mg/l. Evaluate the following set of data obtained by sending the same water sample ve times: 100.67 mg/l, 99.27 mg/l, 97.31 mg/l, 102.95 mg/l, and 202.02 mg/l.


6.1 Data Tables

Hydrochemical studies generate large amounts of data of different parameters obtained in the eld and reported by various laboratories. The rst stage in data processing is to organize the data into tables. This stage is important and warrants some thinking. Have a look at Tables 6.1, 6.2, and 6.3. They contain the same data, but differ in their structure. Which of the three tables is impossible and which is most handy and most informative? Table 6.1 has no caption that relates the data to specic wells or springs, the analytical units are not specied, and the data are arranged in increasing order of the sample number, which has no meaning. Table 6.1 is useless. Table 6.2 has a caption relating the data to Green Mice Springs; the names of the springs from which the samples were collected; the units (meq/l); the name of the laboratory that determined the dissolved ions; the sum of dissolved ions (TDI); and the range of analytical errors. The columns in Table 6.2 are arranged by having the eld data rst (on the left), followed by the cations, and nally (to the right) the anions. The lines of Table 6.2 are arranged by increasing concentration of TDI. Table 6.3 is even more organized: the cations are arranged by increasing concentration (K < Mg < Ca < Na), and the anions are arranged by increasing concentrations in the most saline sample (spring H), namely, SO4 < HCO3 < Cl. This order is seen in all the samples, except the rst (spring A). Table 6.3 reveals that one deals with a complex of springs that

Chemical Parameters: Data Processing Table 6.1 Sample no. 71 72 73 74 75 76 77 78 79 K 0.60 1.03 0.02 0.16 0.31 0.75 1.18 0.89 0.46 Cl 9.11 15.5 0.53 2.67 4.82 11.3 17.7 13.3 6.97 Mg 1.78 2.76 0.47 0.80 1.13 2.10 3.08 2.43 1.46 Na 8.10 11.5 0.91 2.71 4.51 9.90 15.3 11.7 6.30 SO4 1.09 1.36 0.73 0.82 0.91 1.18 1.45 1.27 1.00 Ca 2.72 3.84 1.22 1.60 1.97 3.10 4.21 3.47 2.35 HCO3 3.00 4.22 1.36 1.76 2.17 3.41 4.62 3.81 2.59


Temp. (8 C) 21.4 26.1 15.2 16.8 18.3 23.0 27.6 24.5 19.9

have a similar abundance of the dissolved ions, but differ in salinity (TDI) and temperature. There is no one correct way to organize a tablethe optimal solution has to be searched for in each case. Also, tables should not be overloaded splitting data into several tables can be benecial.

6.2 Fingerprint Diagrams

Figure 6.1 is a ngerprint diagram of the data in Table 6.3. In this gure each spring is represented by one line that provides a visual description of

Table 6.2 Chemical Composition of the Green Mice Springs Complex (meq/l) Sample no. 73 74 75 79 71 76 78 72 77 Spring A C E B D I F G H Temp. (8 C) 15.2 16.8 18.3 19.9 21.4 23.0 24.5 26.1 27.6 K 0.02 0.16 0.31 0.46 0.60 0.75 0.89 1.03 1.18 Na 0.91 2.71 4.51 6.30 8.10 9.90 11.7 13.5 15.3 Ca 1.22 1.60 1.97 2.35 2.72 3.10 3.47 3.84 4.21 Mg 0.47 0.80 1.13 1.46 1.78 2.10 2.43 2.76 3.08 Cl 0.53 2.67 4.82 6.97 9.11 11.3 13.4 15.5 17.7 HCO3 1.36 1.76 2.17 2.59 3.00 3.41 3.81 4.22 4.62 SO4 0.73 0.82 0.91 1.00 1.09 1.18 1.27 1.36 1.45 TDI 5.24 10.5 15.8 21.1 26.4 31.7 37.0 38.8 47.5

Big Chemistry Laboratory, Dataland. Temperature measurement error: + 0.28 C; analytical errors are + 2% for Na, Ca, Cl, and HCO3 and + 5% for K, Mg, and SO4.


Chapter 6

Table 6.3 Rearranged Chemical Composition Data of the Green Mice Springs Complex (meq/l) Sample no. 73 74 75 79 71 76 78 72 77 Spring A C E B D I F G H Temp. (8 C) 15.2 16.8 18.3 19.9 21.4 23.0 24.5 26.1 27.6 K 0.02 0.16 0.31 0.46 0.60 0.75 0.89 1.03 1.18 Mg 0.47 0.80 1.13 1.46 1.78 2.10 2.43 2.76 3.08 Ca 1.22 1.60 1.97 2.35 2.72 3.10 3.47 3.84 4.21 Na 0.91 2.71 4.51 6.30 8.10 9.90 11.7 13.5 13.3 SO4 0.73 0.82 0.91 1.00 1.09 1.18 1.27 1.36 1.45 HCO3 1.36 1.76 2.17 2.59 3.00 3.41 3.81 4.22 4.62 Cl 0.53 2.67 4.82 6.97 9.11 11.3 13.4 15.5 17.7 TDI 5.24 10.5 15.8 21.1 26.4 31.7 37.0 38.8 47.5

Big Chemistry Laboratory, Dataland. Temperature measurement error: + 0.28 C; analytical errors are + 2% for Na, Ca, Cl, and HCO3 and + 5% for K, Mg, and SO4.

the relative abundance pattern of the dissolved ions (the shape of each line) and the relative salinity (the position of the line at the upper or lower part of the diagram). Each line is the compositional imprint of a water sample, and various samples can be compared to each other in the way people can be sorted and identied by their ngerprints. It was Schoeller who, in 1954, applied a ngerprint diagram for the rst time in relation to groundwater analyses. The ngerprint diagram is a most powerful tool in the hands of the hydrochemist, provided that it is done with good thinking regarding the following points.

6.2.1 The Logarithmic Concentration Axis

The set of data in Table 6.4 was generated so that the concentration of dissolved ions increases from data set 1 to set 5, but the relative abundance of the ions is preserved (check it, for example, by comparing the Mg:Ca ratio in data sets 15, Table 6.4). This imitates dilution of a saline water by different amounts of a fresh (ideally, distilled) water, a common occurrence in nature. The data of Table 6.4 have been plotted once with a linear concentration axis (Fig. 6.2) and once with a logarithmic concentration axis (Fig. 6.3). The outcome is striking: the same data plotted with a different concentration axes reveal intrinsically different patterns. On the linear plot the lines of the individual water samples differ in their gradients, whereas on the semilogarithmic plot the lines have the same gradients. The latter well reects the dilution of saline water with fresh water, whereas the former

Chemical Parameters: Data Processing


Fig. 6.1 A ngerprint diagram of the data of Table 6.3. Cations are by convention plotted on the left and anions on the right. In Fig. 6.5 the same data have been replotted in increasing order of cation concentration and decreasing order of anion concentration. Table 6.4 Synthetic Data Generated to Simulate Dilution of a Saline Water by a Fresh Water (meq/l) Data set 1 2 3 4 5 K 0.2 0.4 0.6 0.8 1.0 Mg 0.8 1.6 2.4 3.2 4.0 Ca 1.4 2.8 4.2 5.6 7.0 Na 2.6 5.2 7.8 10.4 13.0 SO4 0.3 0.6 0.9 1.2 1.5 HCO3 2.4 4.8 7.2 9.6 12.0 Cl 2.3 4.6 6.9 9.2 11.5 TDI 10.0 20.0 30.0 40.0 50.0


Chapter 6

Fig. 6.2 A linear ngerprint diagram of samples that resulted from different degrees of dilution of a saline water (Table 6.4). The data reveal compositional lines of different patterns, although their relative ion abundance is the same.

diagram is misleading in giving the impression that each of the plotted water samples has its own relative ion abundances. For this reason a logarithmic vertical axis should always be used to produce ngerprint diagrams.

Fig. 6.3 The data of Fig. 6.2 (Table 6.4) replotted on a semilogarithmic axis. Parallel lines of the same pattern are obtained, well reecting different degrees of dilution of the same saline water.

Chemical Parameters: Data Processing


The advantage of the logarithmic concentration axis is that it provides equal room for ions of low concentration as for ions of high concentration: the distance between the K points of samples 1 to 5 on Fig. 6.3 equals the distance between the Na points of samples 1 to 5not so in the linear concentration diagram (Fig. 6.2), in which the K and SO4 points are densely packed and the Na and Cl points are widely spread.

6.2.2 Selecting the Right Number of Cycles in the Semilogarithmic Diagram

The number of cycles needed is determined by the lowest concentration value and the highest concentration value in the data set. For example, in Table 6.3 the lowest concentration value is the K concentration in spring A (0.02 meq/l) and the highest is the Cl concentration in spring H (17.7 meq/l). Thus four logarithmic cycles were needed to plot the data of Table 6.3 in the ngerprint diagram of Fig. 6.1 (check it). Looking at the data of Table 6.4, how many logarithmic cycles are needed to draw the ngerprint diagram? (The answer is given in Fig. 6.3). Examples of different semilogarithmic papers are given in Fig. 6.4 in order to illustrate the selection of the proper number of logarithmic cycles.

6.2.3 Selection of the Order of Ions on the Horizontal Axis

Figures 6.1 and 6.5 portray the data of Table 6.3, the difference being the order of the ions on the horizontal axis: the cations are arranged in increasing order of concentration, and the anions are arranged in decreasing order of concentration. In this way the cation and anion lines gain a symmetry and are easy to follow (imagine Fig. 6.5 with the anions arranged in increasing order of concentrationswhat would be the outcome?).

6.2.4 Separation of Cations and Anions

As a convention it is suggested that the cations be plotted to the left and the anions to the right of the ngerprint diagram. This separation is in accordance with geochemical thinking: waters are described by the concentration order of the cations and anions (section 6.9) and water rock interactions are discussed by cations and balancing anions. For clarity it is recommended that there be two line segments for each water samplea line connecting all cations and a separate line connecting all anions, as in Figs. 6.3 and 6.5.


Chapter 6

Fig. 6.4 Semilogarithmic papers with 1, 2, 3, 4, and 5 cycles. The 5-cycle is most convenient for the majority of hydrochemical data processing tasks.

Chemical Parameters: Data Processing


Fig. 6.5 Fingerprint diagram of the same data as in Fig. 6.1 (Table 6.3), but cations are arranged in an increasing order of concentration, and anions are arranged in a decreasing order of concentration, resulting in simple lines that can readily be compared.

6.2.5 A Methodological Note

The discussed mode of construction of ngerprint diagrams has been found by this writer to be most informative. Other combinations of the ngerprint diagram principles are in use by various investigators. As a result, different types of ngerprint diagrams are included in the discussion of case studies in the following chapters.

6.3 Composition Diagrams

Pairs of measured parameters may be plotted in x-y diagrams, or composition diagrams. These may be closely placed on one page, as shown in Fig. 6.6 for the data given in Table 6.3. The compositional diagram of Fig. 6.6 portrays the Green Mice Springs data in a visual form. The following features can be observed: the springs vary considerably in their


Chapter 6

Fig. 6.6 A composition diagram of the Green Mice Springs (Table 6.3). Concentrations are given in meq/l. The compositional interrelations of the nine springs are clearly exhibited: mixing lines indicate a saline warm end member mixes in various proportions with a fresh cold end member.

concentrations, and the data plot on straight lines, revealing a positive correlation between K, Na, Ca, Mg, Cl, HCO3, and SO4 with the TDI. Similarly, the temperature is seen to be positively correlated with the TDI. The composition diagram provides a handy way to visually express large amounts of data, complementing the ngerprint diagram. Each type of diagram has its advantages.

6.4 Major Patterns Seen in Composition Diagrams

Let us plot chlorine against TDI with data obtained from samples collected in regional studies carried out on different water sources. The following patterns are possible:

Chemical Parameters: Data Processing


Fig. 6.7 A cluster pattern in a set of composition diagrams of ve adjacent springs. The pattern indicates one type of water is involved. The more parameters that are checked, the higher is the condence of the conclusion.

A cluster (Fig. 6.7). Chloride concentrations in ve adjacent springs reveal a cluster when plotted against TDI. This may indicate all ve springs are fed by one type of water, or in hydrological terms, the ve springs are fed by the same aquifer. One may argue that different waters are involved, each having the same chlorine concentration. Therefore, other parameters are plotted as well, Ca and SO4 in the example of Fig. 6.7. If the same pattern of a single cluster is obtained, the conclusion of one type of water is conrmed. Two clusters (Fig. 6.8). Two clusters of springs are revealed in Mg, Na, and temperature plots versus Cl. Two water groups emerge: (1) a group of ve springs is fed by a water that has relatively higher Mg, Na, and Cl concentrations and is relatively cold and (2) a group of three springs fed by water with relatively lower Mg, Na, and Cl concentrations and a higher temperature. Also, three or more water groups may be reected in composition diagrams.

Fig. 6.8 Two clusters in a set of eight adjacent springs. The pattern indicates two distinct types of water occur in the studied region (with no intermixing): a water type of low Cl, Mg, and Na and an elevated temperature, and a water type of high Cl, Mg, and Na and a low temperature.


Chapter 6

Fig. 6.9 Data from a well eld plotting in straight lines in composition diagrams. These are mixing lines, of which three variations are shown: (a) the line extrapolates to the zero points, indicating mixing of a saline water with a water that has negligible SO4 concentrations (dilution); (b) the line extrapolates to a point in the TDI axis, indicating the fresher end member contains signicant concentrations of ions other than SO4; and (c) the line extrapolates to the SO4 axis, indicating both intermixing waters contain signicant concentrations of SO4.

Data plotting on lines. This type of pattern is shown in Fig. 6.9ac. Such lines may be of different kinds: Fig 6.9a depicts a line extrapolating to the zero point; Fig. 6.9b shows a line extrapolating to a value on the TDI axis; and Fig. 6.9c extrapolates to a value on the vertical axis. Such lines are formed by mixing fresh and saline water in various percentages, for example, intermixing of water ascending from depth with seasonal rain and snowmelt recharge. The topic is further discussed in sections 6.6 and 6.7. Triangular distribution. Occasionally data plot in triangles in composition diagrams, as seen in Fig. 6.10. Such a distribution points to intermixing of three distinct water types: A water type of low TDI, high Na, and low Mg and Cl A water type of medium TDI with low Na and high Mg and Cl A water type of high TDI, high Na, low Mg, and medium Cl

Fig. 6.10 Data of a group of wells falling in triangular areas on compositional diagrams, indicating three distinct water types intermix in varying proportions.

Chemical Parameters: Data Processing


Fig. 6.11 Compositional diagrams of a set of well samples: (a) random SO4 distribution; (b) a positive ClTDI correlation; and (c) a constant HCO3 value. Possible interpretation: mixing of fresh and saline end members that both have the same HCO3 concentration; the SO4 measurements are suspected to be erroneous and should be repeated.

Random distribution. Figure 6.11a shows data of a studied region that reveal a random distribution on a composition diagram. Random distributions of data may indicate . . The measured samples are from nonrelated water sources of different compositions. The analytical quality of the data is poor.

The latter case may be established if other pairs of parameters show a distinct pattern. In the example of Fig. 6.11, the SO4 reveals a random distribution as a function of TDI, but Cl and HCO3 reveal distinct patterns of mixing between fresh and saline end members. Thus the SO4 values are suspected as erroneous, and this parameter has to be remeasured to check for a distinct pattern.

6.5 Establishing Hydraulic Interconnections 6.5.1 Direct Proofs for Hydraulic Interconnections
If dyes injected into one well are then found in an adjacent well, this directly proves hydraulic interconnections and the direction of groundwater ow. Fungal spores, salt, and various radioactive isotopes have been used to trace groundwater ow. A drop in the water table as a result of pumping in an adjacent well is another direct proof of hydraulic interconnections. The drawback of these methods is that they can be traced over small distances, on the order of tens to hundreds meters, and even that requires substantial effort. For greater distances, other indirect tracing methods are


Chapter 6

at our disposal. But rst let us see why it is important to establish hydraulic interconnections.

6.5.2 Water Level Gradient: A Necessary Condition for Determining Flow Direction, but Not a Sufcient One
Water ows from high points to low points, and hence a water level gradient is an essential condition for underground ow. A common practice among hydrologists is to reconstruct groundwater ow directions based on water level gradients (section 4.3). However, a glance at Figs. 6.126.14 reveals that a gradient is a necessary but insufcient condition. Figure 6.12 portrays three wells tapping the same aquifer, and the water ows from the region of well I to well II and on to well III, down-gradient. In Fig. 6.13 three wells manifest a relatively high water table at well I, a medium water table at well II, and a relatively low water table at well III. However, the three wells are not interconnected; they are separated by aquicludes. The three wells shown in Fig. 6.14 are separated by a buried anticline disconnecting well I from wells II and III, in spite of the apparent water table gradient. Wells II and III are hydraulically interconnected. As already mentioned in section 4.4, one can never deduce ow directions from water levels alone.

Fig. 6.12 Three wells tapping the same aquifer. Water ows down-gradient from the area of well I to well II and on to well III.

Chemical Parameters: Data Processing


Fig. 6.13 Three wells with water tables similar to those seen in Fig. 6.12 but separated by aquicludes. They have no hydrological connections in spite of the apparent water table gradient.

6.5.3 The Use of Groundwater Parameters to Establish Hydraulic Interconnections

The patterns of data point distribution on composition diagrams, discussed in section 6.4, provide the means to check hydraulic interconnections: Clustering around a single value, as in Fig. 6.7, indicates that sampled springs have the same type of water and are, therefore, most likely interconnected. Several clusters, as in Fig. 6.8, indicate separate hydraulic systems are involved, each having distinct water types and isolated from the others.

Fig. 6.14 Three wells with an apparent water table gradient of well I > well II > well III. However, a concealed folded structure isolates well I from wells II and III.


Chapter 6

Data plotting on mixing lines, as in Fig. 6.9, is likely to indicate mixing of two water types in various proportions, a topic further discussed in the next section. Mixing of two (or more) water types indicates that at some point two separated water systems are interconnected, either naturally or by drilling. The same holds true for triangular data patterns on composition diagrams, indicating three distinct water types are interconnected.

6.5.4 A Practical Example of Hydrochemical Identication of Separated Groundwater Systems

The data of Table 6.5 are plotted on a ngerprint diagram in Fig. 6.15. Three water groups emerge: A, B, and C. The groups are homogeneous, the samples of each group having nearly the same ion concentrations. Figure 6.16 depicts the data of Table 6.5 in composition diagrams. The three distinct composition groups are well seen. Now that a compositional picture has been gained, Table 6.5 may be reorganized by water groups and by increasing concentrations of cations and anions. The outcome (Table 6.6) is informative and reects the composition pattern of the Hot Fudge wellsthey are not fed by one uniform aquifer, but tap three distinct groundwater systems. The wells of group A are most likely hydraulically interconnected, and so are the wells of group B and of group C. But the water systems A, B, and C are not hydraulically connected.

Table 6.5 Dissolved Ions in the Hot Fudge Well Field (meq/l) Sample no. 1 2 3 4 5 6 7 8 Na 7.2 3.8 4.5 11.5 6.9 11.0 7.5 12.0 Cl 8.1 4.5 5.2 11.0 8.2 12.0 8.6 11.5 SO4 0.52 3.1 3.7 5.4 0.84 6.0 0.60 5.8 Mg 1.5 2.2 2.7 4.0 1.2 4.6 1.8 4.4 HCO3 3.8 5.6 5.1 9.5 3.1 8.8 4.2 8.3 Ca 3.7 6.0 5.5 7.2 4.0 8.3 4.1 7.8 K <0.02 1.2 1.0 2.7 0.04 2.7 <0.02 2.4

Good Day Laboratory; analytical errors: + 4% for K, Mg, Ca, SO4, and HCO3.

Chemical Parameters: Data Processing


Fig. 6.15 A ngerprint diagram of the data of Table 6.5. Three distinct compositional groups emerge: A, B, and C (seen also in Fig. 6.16).

The next stage deals with a search for the geological, hydrological, or geographical meaning of the observed composition groups, turning them into geochemical groups.

6.6 Mixing Patterns

The data given in Table 6.4 were generated by mixing the water of set 1 (fresh) with the water of set 5 (more saline). The fraction (x) of type 5 water in the various samples may be calculated by applying each of the parameters of Table 6.4. For example, applying the K values, the fraction of type 5 water in set 3 is 1.0x 0.2(1 x) 0.6, hence, x 0.50, or set 3 contains 50% of type 5 water and 50% of type 1 water. (Calculate the fraction of type 5 water in set 3, applying the respective concentrations of Ca, Na, and Cl. Is the value obtained with K conrmed?) The calculation of mixing percentages is further discussed in the next section. The series of synthetically generated mixtures of two water types given in Table 6.4 is drawn in Fig. 6.3 in a ngerprint diagram on semilogarithmic


Chapter 6

Fig. 6.16 Composition diagrams of the data of Table 6.5. Three distinct compositional water groups emerge: A, B, and C.

paper. The data plot on parallel lines, reecting the dilution of a saline water type with a salt-devoid fresh water. The same data are plotted on a composition diagram in Fig. 6.17. The data plot on straight mixing lines that extrapolate to the zero points. In contrast, the lines in Fig. 6.6 do not extrapolate to the zero points, indicating mixing of two water types, each containing a signicant concentration of dissolved ions. Thus a glance at a composition diagram reveals . The occurrence of mixing (straight lines)

Chemical Parameters: Data Processing Table 6.6 Reorganized table of the Hot Fudge data (Table 6.5) (meq/l) Group A Sample no. 1 7 5 2 3 8 4 6 K < 0.02 < 0.02 0.04 1.2 1.0 2.4 2.7 2.7 Mg 1.5 1.8 1.2 2.2 2.7 4.4 4.0 4.6 Ca 3.7 4.1 4.0 6.0 5.5 7.8 7.2 8.3 Na 7.2 7.5 6.9 3.8 4.5 12.0 11.5 11.0 SO4 0.52 0.60 0.84 3.1 3.7 5.8 5.4 6.0 HCO3 3.8 4.2 3.1 5.6 5.1 8.3 9.5 8.8 Cl 8.1 8.6 8.2 4.5 5.2 11.5 11.0 12.0


TDI 24.8 26.8 24.3 26.4 27.7 52.2 51.3 53.4


. .

Dilution of a saline water with fresh water (extrapolation to the zero points) Mixing of two water types, both with a load of dissolved ions (lines extrapolating to one of the axes)

The patterns in a ngerprint diagram provide the same information: . . Parallel lines (e.g., Fig. 6.3) indicate dilution occurs. Lines with a fan shape (e.g., Fig. 6.5), caused by progressive changes in concentrations and relative abundance, indicate mixing of two water types.

Fig. 6.17 Composition diagrams of the data of Table 6.4 (in meq/l). The data have been computed to represent different mixing ratios between water of type 5 and distilled water. The data plot on straight mixing lines that extrapolate to the zero points.


Chapter 6

6.7 End Member Properties and Mixing Percentages 6.7.1 Hydrologically Deducible End Members
A group of springs, Kaneh-Samar, issues at the Dead Sea shore. Results of a hydrochemical study are given in Table 6.7 and plotted in Fig. 6.18, revealing mixing lines. Contributions from the adjacent Dead Sea were suspected. Thus the Dead Sea values were entered into the Kaneh-Samar composition diagrams of Fig. 6.18. Since the Dead Sea values fall on the same line as the Kaneh-Samar data, the role of the Dead Sea as the saline end member is established. The procedure has been repeated for four different ions (Fig. 6.18), and the conclusion is therefore reached with a high degree of condence. The fresh end member, in this case, is recharged in the

Fig. 6.18 The Kaneh-Samar Springs, on the western shore of the Dead Sea. The composition of the Dead Sea water falls on the continuation of the mixing line obtained by the spring data, supporting the initial hypothesis that Dead Sea water is locally intermixed with fresh water (Mazor, 1973). The ion concentrations in the Dead Sea were divided by 1/25 to accommodate the Dead Sea in the diagram, which had to be designed for the much fresher spring waters.

Table 6.7 Dissolved Ions in the Kaneh-Samar Springs and Dead Sea Brine (meq/l) Li 0.1 0.08 0.13 0.08 0.55 1.21 1.02 1.09 1.27 1.47 1.23 1.30 1.82 1.35 1.02 1.73 1.62 6.3 6.0 4.92 4.49 4.54 5.23 4.75 4.82 5.39 4.8 5.28 5.28 5.49 4.52 5.57 5.79 4.66 4.57 4.66 3.77 3.8 Sr K Na Mg Ca Br Cl Total Total SO4 HCO3 anions cations Total ions Reaction error (%) 1.2 1.2 1.6 1.5 0 4.6 3.4 2.5 2.8 3.7 3.1 4.2 1.6 0.4 1.8 1.1 1.0 0.4 0.3

Chemical Parameters: Data Processing

Sample no.

1 < 0.00014 < 0.08 0.2 1.8 3.2 3.2 < 0.00001 3.3 2 < 0.00014 < 0.002 0.2 1.9 3.6 2.8 < 0.00001 3.7 3 < 0.00014 0.012 0.5 1.9 3.6 3.2 < 0.00001 4.3 4 0.001 0.012 0.4 3.3 5.6 4.4 0.02 8.0 5 0.001 0.016 0.8 4.6 6.8 4.0 0.04 10.9 6 0.01 0.04 1.9 15.2 24.0 8.8 0.32 39.2 7 0.01 0.04 2.0 16.0 22.8 8.8 0.32 39.6 8 0.01 0.04 1.7 16.1 24.8 9.6 0.38 43.4 9 0.02 0.04 2.2 20.0 30.8 12.8 0.52 62.6 10 0.02 0.04 2.7 27.2 34.0 13.6 0.55 64.8 11 0.02 0.04 2.0 19.0 37.2 14.0 0.58 69.7 12 0.03 0.08 3.1 33.9 46.4 14.8 0.79 83.8 13 0.02 0.08 2.4 29.9 45.2 14.8 0.75 87.4 14 0.03 0.08 3.5 32.6 51.6 17.6 0.89 98.3 15 0.04 0.12 3.2 40.7 72.0 22.0 1.29 136.0 16 0.05 0.12 6.4 54.3 94.8 29.6 1.68 181.0 17 0.06 0.16 5.7 65.2 113.2 33.6 2.10 213.0 Dead Sea 2.5 5.9 185.0 1590 3045 687.0 58.0 5486 Dead Sea 2.5 5.9 169.0 1650 3260 756.0 56.0 5814

8.3 8.5 16.8 8.3 8.5 16.8 8.9 9.2 18.1 13.3 13.7 27.0 16.2 16.2 32.4 49.9 49.9 95.4 46.3 49.6 95.9 49.7 52.2 101.9 69.7 65.9 135.6 72.1 77.6 149.7 77.0 72.3 149.3 90.4 98.3 188.7 95.5 92.4 187.9 106.3 105.4 211.7 143.3 138.1 281.4 189.3 185.3 374.6 222.1 217.9 440.0 5554.0 5515.0 11069.0 5880 5843 11723

Source: Mazor et al. (1973).



Chapter 6

Judean Mountains, with a salinity that is negligible compared with the Dead Sea brine, so one actually talks of dilution. Examples of hydrologically deducible end members include dams that contribute to adjacent wells and seawater intruding into coastal aquifers. Known sources of manmade pollution may be treated as hydrologically suspected end members.

6.7.2 Calculating Mixing Percentages

Once the end members are identied, their mixing ratios can be calculated, as discussed in section 6.6. Dealing with real data of complex natural systems, the calculations of mixing percentages warrant some discussion. Table 6.8 contains calculations of the percentages of Dead Sea water in each Kaneh-Samar spring (Table 6.7). It is seen that the percentages derived via the various parameters somewhat differ from each other due to analytical errors and, possibly, due to superposition of secondary processes. The average value may be taken as best representing the true values (last column in Table 6.8).

Table 6.8 Percentages of Dead Sea Brine Diluted by Fresh Water in the KanehSamar Springs (based on the data of Table 6.7), Calculated from the Concentrations of Various Dissolved Ions Sample no. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Na 0.11 0.12 0.12 0.20 0.28 0.94 0.99 1.0 1.2 1.7 1.2 2.1 1.8 2.0 2.5 3.4 4.0 Mg 0.10 0.11 0.11 0.17 0.22 0.76 0.72 0.79 0.98 1.1 1.2 1.5 1.4 1.6 2.3 3.0 3.6 Cl 0.06 0.07 0.08 0.14 0.19 0.70 0.71 0.78 1.1 1.2 1.2 1.5 1.6 1.8 2.4 3.2 3.8 Br 0.67 0.91 0.97 1.0 1.4 1.3 1.6 2.3 3.2 3.6 Average 0.09 + 0.02 0.08 + 0.03 0.08 + 0.02 0.17 + 0.02 0.23 + 0.03 0.80 + 0.09 0.81 + 0.12 0.81 + 0.10 1.0 + 0.10 1.2 + 0.2 1.2 + 0.1 1.6 + 0.2 1.5 + 0.2 1.8 + 0.2 2.4 + 0.1 3.2 + 0.1 3.8 + 0.3

Chemical Parameters: Data Processing


6.7.3 Extrapolated End Members

Mixing lines can also be of negative correlations, as, for example, for saltpoor warm water mixing with a saline cold end member (Fig. 6.19). In such a case the maximum possible temperature of the warm end member can be deduced by extrapolating the best-t line to zero TDI. A value of 468 C is obtained in the example shown in Fig. 6.19. The temperature of the true warm end member lies between the warmest measured value and the extrapolated value. In the example given in Fig. 6.19, these two values are rather close: 39 and 468 C, respectively. Negative correlations in mixed groundwater systems are often obtained with tritium and 14C data plotted versus dissolved ions (old saline water diluted by recent fresh water). The value of tritium and 14C in this respect will be demonstrated in sections 10.6 and 11.10.

6.7.4 Mixings Deduced from Contradicting Parametric Combinations

Dissolved free oxygen is characteristic of well-aerated groundwater, whereas dissolved H2S is characteristic of anaerobic conditions. Thus water contains either dissolved free oxygen or H2S. Yet, in special cases, both constituents are found in signicant concentrations as a result of last minute mixing. A second example of a contradicting combination is occasionally observed in groundwaters with small amounts of 14C and signicant

Fig. 6.19 A negative linear correlation between temperature and TDI in a group of springs. By extrapolation, the highest possible temperature value of the warm end member is 468 C. The real temperature of the end member lies between the warmest measured spring and the extrapolated value.


Chapter 6

amounts of tritium. The rst feature, small amounts of 14C, indicates an old age of several thousands years, whereas large amounts of tritium indicate water recharged postnuclear bomb tests, that is, after 1953. The use of tritium and 14C as age indicators is discussed in Chapters 10 and 11. Water cannot be old and young at the same time, and the combination of small amounts of 14C and large amounts of tritium can result only from mixing of old and young waters.

6.8 WaterRock Interactions and the Types of Rocks Passed

The bearing of lithology on water composition was discussed in section 3.1 and summed up in Table 3.1. These points deserve further attention.

6.8.1 WaterRock Interactions Induced by CO2

The concentration of CO2 in the atmosphere is 0.03% by volume. In the soil air, that is, the air between the soil grains, the concentration of CO2 is 50 to 100 times higher. The source of the extra CO2 is biogenic: respiration of plant roots and bacterial decomposition of buried plant remains. Distilled water is fairly nonreactive and practically does not interact with carbonates or silicates, such as limestone; dolomite and marl; or granite, basalt, or sandstone. However, when enriched with CO2, water turns into carbonic acid and can dissolve rocks by means of the reaction CaCO3 H2 O CO2 $ CaHCO3 2 limestone bicarbonatesoluble The double arrows indicate the reaction can go both ways: to the right, dissolution of limestone is described; to the left, precipitation of limestone is described. A high supply of CO2 drives the reaction to the right (limestone dissolution, as in the forming karstic conduits); depletion of CO2 drives the reaction to the left (precipitation of calcite and aragonite, as in the formation of stalactites and stalagmites). The result of CO2-induced limestone dissolution is groundwater with calcium as a signicant dissolved cation and HCO3 as a signicant anion. The maximum concentration of these ions is, however, limited by the saturation value of calcite in aqueous solutions. Therefore, groundwater in limestone terrains is commonly of good quality.

Chemical Parameters: Data Processing


Carbon dioxide also induces interactions of water with silicate rocks: 2KAlSi3 O8 6H2 O CO2 ?Al2 Si2 O5 OH4 4SiOOH2 K2 CO3 potassium clay soluble soluble feldspar Ca; Fe; MgSiO3 2H2 O 2CO2 ?Ca; Fe; MgHCO3 2 SiOOH2 pyroxene soluble soluble Thus, water containing HCO3 indicates CO2-induced interactions with rocks, and the balancing cations indicate the types of rocks passed: calcium comes from interaction with limestone, and calcium and magnesium together come from interaction with dolomite; potassium and, even more often, sodium in bicarbonate water come from silicate rocks rich in potassium or sodium feld-spars.

6.8.2 The Diagnostic Value of Dissolved Ions and Cations

The discussions in this chapter and in section 3.1 and the data in Table 3.1 reveal the diagnostic value of anions as indicators for the dominant rock types through which a given groundwater has passed: . . . . . Highly saline groundwater, containing chlorine on the order of 180,000 mg/l, and containing sodium as the dominant cation, indicates that halite is present in the aquifer rocks. Relatively fresh groundwater that contains chlorine in concentrations that indicate undersaturation with respect to halite indicates this mineral is absent in the host rocks. SO4-dominated water with concentrations of more than 2300 mg/l, and containing equivalent concentrations of calcium, indicates that gypsum or anhydrite is present in the aquifer rocks. Groundwater that is distinctly undersaturated with respect to gypsum indicates this mineral is absent in the aquifer rocks. Bicarbonate-dominated water with TDI concentrations up to about 600 mg/l has not passed evaporites, and the nature of the rocks interacted with can be deduced from the cations: calciumdominated HCO3 water has passed limestone; calcium- and magnesium-dominated HCO3 water is produced by contact with dolomite; sodium-dominated and potassium-rich HCO3 waters have interacted with feldspar, plagioclase, and pyroxene contained in igneous or volcanic rocks.


Chapter 6

The discussion on the application of dissolved ions as indicators of the rocks passed through by groundwater is of a generalized natureto show the direction of hydrochemical thinkingand is useful in establishing the constrains needed to formulate phenomenological conceptual hydrological models (section 1.5). The topic of chemical waterrock interactions is discussed by Drever (1982), Erikson (1985), and Hem (1985).

6.9 Water Composition: Modes of Description

Chemical data may be presented in tables and in graphs, but we also need ways to describe the chemical composition of water in written texts. This can be done in various ways: Dominant cations and anions. Water can be described by its dominant cation and dominant anion. For example, the water of spring A in Table 6.3 has calcium as the dominant cation and HCO3 as the dominant anion, or the water is of a CaHCO3 type. Similarly, the water of spring H in Table 6.3 is of a NaCl type. Order of cation and anion concentrations. A more detailed description of water composition includes the relative abundance of cations and anions. The example of spring A in Table 6.3 can be described as Ca > Na > Mg 4 K and HCO3 > SO4 > Cl

Chlorinity, total dissolved salts, and total dissolved ions. The concentrations of chemical compounds can be expressed in various ways: . . . Chlorinitythe concentration of chlorine Total dissolved salts or solids (TDS)the amount of all chemical constituents, determined via electrical conductivity measurements, often called salinity. Total dissolved ions (TDI)the sum of dissolved cations and anions.

Mode of composition description: by equivalents or by weight per volume of water. Each description of water composition has to be accompanied by a statement of the units in which the data applied have been expressed, such as meq/l or mg/l. This point is demonstrated by the following set of data:

Chemical Parameters: Data Processing K In meq/l In mg/l 0.10 3.9 Na 5.1 117 Mg 2.5 30.2 Ca 1.8 36.0 Cl 5.2 185 SO4 0.3 14.4 HCO3 4.7 225

139 TDI 19.7 611

This water can be described in the following two ways: Na > Mg > Ca 4 K ; Cl > HCO3 > SO4 in equivalents per volume of water Na > Ca > Mg 4 K ; HCO3 > Cl > SO4 in weight per volume of water It is important to notice that the order of the ions is different in the two modes of expression, and therefore the units applied have to be specied. The same holds true for chlorinity, TDS, or TDI. The TDI value of the above example is 19.7 meq/l or 611 mg/l. Water description by its quality or usefulness. Examples: . . . . . . Potable waterup to 600 mg/l TDI. Slightly saline water, adequate for drinking and irrigationup to 1000 mg/l TDI. Medium saline water, potable only in cases of need, can be used for irrigation of special crops and sh raisingup to 2500 mg/l TDI. Saline water, adequate for sh raising and industrial useup to 5000 mg/l. Brackish waterup to TDI of seawater, or 35 g/l. Brinemost saline water, with TDI higher than seawater.

6.10 Compositional Time Series

The chlorine concentration has been repeatedly measured in a well, as shown in Fig. 6.20. What hydrological conclusions may be reached? Two water types, of different chlorine concentrations, intermix. What is the nature of this mixing? To answer this question, the nature of the time periodicity has to be discussed. A case study of this kind has been reported by Tremblay et al. (1973) from a coastal well on Prince Edward Island (Fig. 6.21). It was pumped daily from 8 a.m. to 5 p.m., and the chlorine concentration was measured at these hours. The chlorinity increased during the day and dropped until the following morning. This simple series of


Chapter 6

Fig. 6.20 Repeated chlorine measurements in the same water source (well or spring). Mixing of two water types is revealed.

observations revealed that seawater was drawn into the well due to overpumping, but the inow of fresh water was sufcient to suppress the seawater intrusion overnight. Hence, if the higher chlorine concentration is not wanted, the pumping rate must be reduced. This practical conclusion could be reached by a simple series of repeated chlorine measurements, whereas a single analysis could not reveal the dynamics of this water system. It would be desirable to check this conceptual model by repeated measurements of additional parameters. Wilmoth (1972) reported chlorine measurements in a group of wells in Charleston, West Virginia (Fig. 6.22). A gradual chlorine increase occurred from 1920 to the end of 1950, when pumping was ended. A check in 1970 revealed that the wells have nearly returned to their original chlorinity. Wilmoth concluded that saline water, underlying the pumped fresh water aquifer, gradually migrated upward due to the pumping. This is another

Fig. 6.21 Chloride measurements in a coastal well on Prince Edward Island. The well was operated daily from 8 a.m. to 5 p.m. and it was analyzed at these times: 8 p.m. (circles) and 5 p.m. () (following Tremblay et al., 1973). Encroachment of seawater was concluded, with immediate bearing on management (see text).

Chemical Parameters: Data Processing


Fig. 6.22 Changes in chlorine concentration in groundwater of an overdeveloped aquifer, Charleston, West Virginia (from Wilmoth, 1972).

example of the value of repeated measurements, further discussed in section 7.6. This is also a demonstration of the value of historical data, further discussed in section 7.5.

6.11 Some Case Studies

No case study is exactly like another case. Each case study has its own features, dened by the natural setting and the nature of data obtained. The following case studies are an assortment of studies, heavily based on chemical data.

6.11.1 Seawater Encroachment

Cotecchia et al. (1974) studied the salinization of wells on the coast of the Ionian Sea. A ngerprint diagram (Fig. 6.23) served to dene a conceptual model. The lowest line (MT) is of a fresh water spring and the uppermost line (I.S.) is of the Ionian Sea water. The lines in between (SR and CH) are of groundwaters with increasing proportions of seawater intrusion. The CH well met the nondiluted seawater at a depth of 170 m. This interpretation seems to be well founded as it is based on six dissolved ions. The whole story is condensed into one ngerprint diagram.

6.11.2 Classication into Lithologically Controlled Geochemical Water Groups

A major application of ngerprint diagrams is in sorting geochemical data into groups. Figure 6.24 represents the results of an extensive study of


Chapter 6

Fig. 6.23 A ngerprint diagram of water in coastal wells of the Ionian Sea (I.S.). MT is a freshwater spring. Well SR has slight contributions of seawater, a feature that is more pronounced in the deeper well (CH), which encountered the seawater at a depth of 170 m. (Data from Cottechia et al., 1974.)

mineral waters in Switzerland (Vuataz, 1981). Three compositional groups emerged: Na-SO4, Ca(Na)-HCO3, and Ca-SO4. A search for the geographical, hydrological, or lithological meaning of these compositional groups showed a match with the last factorlithology: the Na-SO4 waters issue in crystalline rocks, the Ca(Na)-HCO3 waters issue in carbonate rocks, and the Ca-So4 waters pass gypsiferous sediments. The next step in such a study may be more quantitative, that is, the conceptual model is checked and worked out with waterrock equilibration equations and calculation of saturation indices with regard to various mineral compositions.

6.11.3 Solubility Control of Groundwater Chemistry in an Arid Region

An extensive study of shallow groundwaters in the Kalahari atland revealed a wide range of concentrations and different compositions. A composition diagram (Fig. 6.25) produced an evolutionary picture. The concentration of HCO3 increased with increasing TDI, and at 10 meq HCO3/l the values leveled off and no further systematic increase in HCO3

Chemical Parameters: Data Processing


Fig. 6.24 Fingerprint diagrams of data obtained in a study of mineral springs in Switzerland (Vuatax, 1982). Three compositional groups emerged: Na-SO4, Ca(Na)-HCO3, and Ca-SO4. In this case lithology was identied as the major control.

concentration was observed, although the TDI increased signicantly. Such a pattern indicates that saturation of a relevant salt controls the concentration of the respective ions.


Chapter 6

Fig. 6.25 Composition diagrams of an extensive study of shallow groundwaters in the Kalahari atland (Mazor, 1979). HCO3, SO4, Ca, and Mg increase with increasing TDI in the left part of the diagrams, and then level off at the saturation values for Ca and Mg carbonates and gypsum. In contrast, Na and Cl are low at the lower TDI range and then increase with TDI, indicating that the higher salinization is caused by the more soluble NaCl.

In the Kalahari study saturation with regard to calcium and magnesium carbonates was suggested. This conclusion was supported by . . Equilibrium calculations that revealed that the waters with 10 meq HCO3/l were saturated with regard to limestone and dolomite. Calcretes (CaCO3 crusts) are common in the investigated area.

The SO4 concentration is seen in Fig. 6.25 to be low in the range of HCO3 increase, that is, up to 40 meqTDI/l. At higher TDI values the SO4 rises, but it levels off at about 20 meq/l, which is the saturation value with regard to gypsum. Sodium and chlorine are low in Fig. 6.25, up to 40 meqTDI/l, and then increase linearly with TDI. This was explained by dissolution of NaCl. All of the studied waters, even the most saline ones, were below NaCl saturation. The observations discussed in light of the composition diagrams lead to the following conceptual model for the Kalahari groundwaters:

Chemical Parameters: Data Processing


inltrating rainwater is enriched in soil CO2 and interacts with feldspars in the covering Kalahari sand. As a result, the water is enriched with HCO3 that is balanced by calcium, magnesium, and some sodium. In waters that become more saline, saturation of carbonates is reached and calcretes are formed. Another source of salts is rainborne and windborne sea spray, common over all continents. Substantial evaporation causes these salts to concentrate in the soil, and they are partially washed down with the fraction of rainwater that inltrates into the saturated groundwater zone. In summary, the evolution of the Kalahari groundwaters is controlled by the solubility of the relevant minerals, which is Ca; Mg CO3 < CaSO4 5 NaCl

6.11.4 Mixing of Cold and Warm Waters

In a study of the spring complex of Combioula, southern Switzerland, samples were repeatedly taken and all the data were summarized in a composition diagram (Fig. 6.26). Mixing lines are indicated at Li, Na, K, Mg, SiO2, TDS, and temperature, plotted as a function of Cl. Thus a cold fresh water mixes with ascending warm saline water. Horizontal lines are seen for Ca, Sr, and especially for HCO3, indicating these ions occur in both water end members in the same concentrations. The perfect shape of the Li, Na, K, Mg, HCO3, and temperature lines in Fig. 6.26 indicates that only one warm water and one cold water are involved in the intermixing. The beauty of this conceptual model lies in its explanation of dozens of different observed water temperatures and ion concentrations as mixings of only two end members.

6.12 Saturation and Undersaturation with Regard to Halite and Gypsum: The Hydrochemical Implications
Water brought in contact with halite readily dissolves it. If the amount of halite is great, as compared to the amount of water, saturation is reached in a matter of a few days, at which time maximal chlorine dissolution takes place, reaching concentrations of more than 180,000 mg/l. Halite is the sole source of chlorine that water has by interaction with rocks. Hence chlorine concentrations in groundwater of around 180,000 mg/l, balanced mainly by sodium, indicate halite is present in the aquifer rocks. In contrast, groundwater that is signicantly undersaturated with respect to halite indicates that halite is absent from the respective rock system. Most groundwaters contain chlorine in the concentration range of 502000 mg/l


Chapter 6

Fig. 6.26 Repeated measurements in a group of springs at Combioula, southern Switzerland (Vuataz, 1982). Positive correlation lines are seen for Li, Na, K, Mg, TDS, and temperature, plotted as a function of Cl. Mixing of a cold fresh water with ascending warm saline water is indicated.

two to three orders of magnitude below the halite saturation concentration. Thus most groundwaters obtain the bulk of their chlorine from outside the rock systemit is brought in with the recharge water.

Chemical Parameters: Data Processing


Saturation with respect to gypsum (or anhydrite) is reached in a few weeks to a few months, attaining an SO4 concentration of more than 2300 mg/l. Thus such an SO4 concentration, mainly balanced by calcium, indicates gypsum or anhydrite are present in the rock system. In contrast, a lower SO4 concentration indicates undersaturation with respect to gypsum or anhydrite and thus absence of these minerals from the rock system. Most groundwaters contain SO4 in the range of only 20300 mg/l. The observed SO4 is in these cases brought in by the recharge water.

6.13 Sea-Derived (Airborne) Ions: A Case Study Demonstrating the Phenomenon

Seawater has a distinct composition, reected in the concentration of various dissolved ions (Table 6.9). Most groundwaters contain considerably lower ion concentrations than seawater, but the relative abundance of some of the dissolved ions is often similar to the marine abundance. Examples of marine relative ion abundance in shallow unconned groundwaters from a small region of the Wheatbelt, eastern Australia, are portrayed in Fig. 6.27. The area is 600 km inland. Linear positive correlations are seen between Cl and Br, Na, Mg, and to some extent K. Hence, it was hypothesized that the source of the major part of the dissolved ions comes not from waterrock interactions, as these would explain neither the observed pattern nor the wide range of concentrations, but that the bulk of the dissolved ions originate from atmospheric salts. The wide range of concentrations was suggested to reect a wide range of evapotranspiration indices that in turn reect local variability in evapotranspiration conditions. Different degrees of retardation of precipitation at or near the surface result in different degrees of salt enrichment in the recharged water fraction. The values of seawater were added to the composition graphs in Fig. 6.27, and they plotted right on the linear correlation lines of Cl and Br, Na, Mg, and to some extent K. The following conclusions could be drawn: . The dissolved Cl, Br, Na, Mg, and K are of a sea-derived origin, whereas observed excesses of HCO3 and Ca are derived from CO2-

Table 6.9 Average Composition of Seawater (g/1) Na 10.6 Mg 1.3 Ca 0.4 K 0.4 Cl 19.0 SO4 2.6 HCO3 0.12 Br 0.07


Chapter 6

Fig. 6.27 Composition diagrams of shallow observation wells, Merredin region, the Wheatbelt, western Australia (following Mazor and George, 1992). The following observations are made: (1) Cl, Br, Na, Mg, and to some extent K reveal linear positive correlations; (2) the values spread over a wide range of concentrations, indicating a wide range of evapotranspiration intensitives prior to inltration into the saturated zone; (3) the seawater value falls on these lines, indicating the marine relative abundance is well preserved. The data provide a detailed insight into the studied hydrological system (see text).

. . .

induced waterrock interactions of the type described in section 6.8. The formation of sea spray is accompanied by no ionic fractionation. The atmospheric transport of sea-derived salts for hundreds of kilometers causes no ionic fractionation. Evapotranspiration caused ion concentrations to increase up to seawater concentration (Fig. 6.27), maintaining the marine imprint of relative abundance. Thus salts accumulating on the surface at the end of dry periods are effectively dissolved by the following rains and are eventually carried into the saturated groundwater zone. The Wheatbelt region, which included study sites in addition to those reported in Fig. 6.27, is hydrochemically maturethe rocks have seen groundwater with the same composition for a long

Chemical Parameters: Data Processing


enough time so that all potential ion exchange locations have been used upand the soilrock system causes conservative behavior not only for Cl and Br, but also for Na, Mg, and in some cases for K and SO4. The distinct variability in ion concentrations, observed in waters tapped in neighboring wells, placed several kilometers apart, indicates the importance of local recharge as compared to the regional base ow.

The preservation of the marine relative abundance of several ions has similarly been observed for large regions of Victoria and other Australian regions and in other countries. Yet in most setups waterrock interactions and other ionic inputs change the marine relative abundance, as discussed in the following section.

6.14 Sources of Chlorine in Groundwater

Chloride is perhaps the most informative ion from a hydrochemical perspective, as it is common in groundwater, has a limited number of identiable sources, and is hydrochemically conservative. These properties turn chlorine into a most useful hydrochemical marker. Three basic sources of chlorine in groundwater have to be considered in every case study: . Rock salt. Chloride can be contributed by dissolution of halite that is present in the aquifer rocks either as rock salt or as veins crossing other rocks, for example, shale or clay. As stated in section 6.12, this potential source can be ruled out for all groundwaters that are distinctly undersaturated with regard to halite, that is, whenever the chlorine concentration is signicantly less than 180,000 mg/l. Thus this source of chlorine can be ruled out for all fresh groundwater types. This point can be independently checked by the Cl/Br ratio (by weight) in the groundwater: it has to be compared to the marine value of around 293 found in sea spray, in contrast to that of greater than 3000 observed in halite, and thus expected in groundwater that dissolved this mineral. Seawater. Encroachment of seawater into coastal wells is a phenomenon that is limited to within a few kilometers from the seashore. It is noticeable as rising salinity and is connected to overpumping that causes signicant lowering of the local water table. Seawater encroachment disappears with a decrease in the pumping rate and restoration of the local water table. Seawater stored in aquifer rocks since the last coverage of the terrain by the


Chapter 6

sea is unlikely in most situations as ushing of aquifer rocks is fast. This source of chlorine can be ruled out for all fresh groundwaters that are located in terrains with a continental history for at least 1 million years. Sea-derived airborne salts. Also called atmospheric salts, these are the most common source of chlorine in groundwater. The phenomenon was described in the previous section. Atmospheric chlorine is of major importance in all cases where the other sources can be ruled out. Thus atmospheric chlorine dominates in groundwaters that are fresh and are more than a few kilometers distant from the seashore (and in many cases up to the shore as well). Marine abundance ratios of various ions to chlorine supply direct evidence for their origin from atmospheric sea-derived salts, as discussed in section 6.13.

6.15 Evapotranspiration Index: Calculation Based on Chlorine as a Hydrochemical Marker

Chloride is unique as being most conservative among the common ions. Once it is introduced into the groundwater it stays in it, as there exists no waterrock interaction that can remove chlorine from groundwater. Bromide and lithium are similarly conservative, but their concentrations are low in fresh groundwater, and hence they are seldom analyzed. Precipitation is split into runoff and inltrating water. A major part of the inltrating water is returned to the atmosphere by the combined action of evaporation and transpiration (section 2.6), and only a fraction of the water moves deep enough to reach the saturated zone. Evaporation and transpiration are effective on water alone; the contained salts stay behind, dissolved in the fraction of the water remaining in the aerated zone or accumulating on the surface and in the soil at the end of the dry season. The next inltrating rainwater dissolves these salts and pushes them further down. As a result, groundwater systems are recharged by waters with a wide salinity range, reecting at each location the relative amount of water returned to the atmosphere by evapotranspiration. The evapotranspiration index expresses the extent of water loss by evapotranspiration: ET index effectively recharged water=infiltrating water where infiltrating water precipitation7runoff

Chemical Parameters: Data Processing


Chloride is most useful as a semiquantitative marker for the calculation of the evapotranspiration index, using the chlorine concentration in precipitation and its concentration in a studied groundwater. Examples: A chlorine concentration of 5 mg/1 is found in the precipitation of many rainy terrains, but the respective groundwaters often contain around 50 mgCl/l. Thus, ETindex (5/50) 6 100 10%; that is, 10% of the initially inltrating water reaches the saturated zone as effective recharge. A chlorine concentration of 10 mg/l typies precipitation in semiarid zones, along with groundwaters that often contain 500 mg Cl/l. Thus in these terrains ETindex 2%. The complete range of Etindex values spans from about 50% in cold rainy regions to 0.5% in warm zones. Large variations are also observed within each climatic zone as a function of topography and the type of local soil or exposed rock, causing different extents of water retardation at or near the surface, resulting, in turn, in different intensities of evapotranspiration-induced water losses into the atmosphere.

6.16 CO2-Induced WaterRock Interactions Revealed by Chlorine Serving as a Hydrochemical Marker

Composition diagrams of water from wells in Tel Aviv, Israel, are given in Fig. 6.28. Each point represents one analysis in a well, and the triangle denotes the composition of seawater (divided by 10 to t into the diagram). Sodium, magnesium, and even SO4, plotted as a function of chlorine, are seen to fall on lines on which the marine value also falls. This outcome is interpreted as indicating that the bulk of the Cl, Na, Mg, and SO4 originate from sea spray, the differences in composition being produced by different evapotranspiration intensities operating on the local discharge water. In contrast, the calcium and HCO3 values reveal a signicant enrichment as compared to the marine relative abundance, indicating enrichment by waterrock interaction. The reported data were collected from 19341948, when the young city still had a large number of septic tanks in use. These increased the biogenically produced CO2 concentration in the aerated zone, making room for the intensied dissolution of carbonate which occurs as the cement of the local sandstone. The observation that magnesium preserved the marine relative abundance (Fig. 6.28) indicates that the dissolved carbonate was a magnesium-poor calcite, and no dolomite is involved.


Chapter 6

Fig. 6.28 Composition diagrams of 27 wells in the coastal city of Tel Aviv, Israel. Data were repeatedly collected at an early stage of abstraction from 19341948.

6.17 Summary Exercises

Exercise 6.1: The beginning of a new hydrochemical project includes search for existing data. In many cases such data are scarce and incomplete, but something of value can always be learned. In a real case study of water supply to a mine in Botswana, the initial data available were only a score of chlorine measurements that revealed signicant concentration uctuations at sporadically repeated measurements in the same wells. What would you conclude in such a case? How would this inuence your research program? Exercise 6.2: Types of correlation lines seen in composition diagrams are described in section 6.4 and Fig. 6.9. In this light analyze the data plotted in Fig. 6.26. What can be concluded?

Chemical Parameters: Data Processing


Exercise 6.3: Draw a ngerprint diagram of the data of springs A, B, C, and D given in Table 11.8. Interpret the pattern you will obtain in hydrological terms. Exercise 6.4: Table 6.7 presents data of springs located on the shore of the Dead Sea and of the Dead Sea brine. Draw a ngerprint diagram of these data, but omit the rst three samples because they include nonspecic numbers (e.g., < 0.00014) and these cannot be drawn, and apply only the second Dead Sea set of values. How many logarithmic cycles are needed? Interpret the data in hydrological terms. Exercise 6.5: Draw a new ngerprint diagram of the data given in Table 6.7 (without the rst three samples and using only the second Dead Sea set of values), but this time divide the Dead Sea values by a factor of 10. Compare this diagram with that you have obtained in the last exercise. Is there an improvement? What is it? Exercise 6.6: Fig. 6.22 describes repeated chlorine measurements in a well tapping an overpumped aquifer, in Virginia. Which operational conclusions can be drawn on the basis of this simple set of data? Exercise 6.7: Working with archive data, it is often necessary to draw conclusions from incomplete graphic material. Fig. 6.29 summarizes chemical data of six samples collected from a spring over 5 years. The gure is contained in a report and no units are given (mg/l or meq/l). Try to retrieve as much hydrological information as possible. Exercise 6.8: Study the ngerprint diagram of Fig. 6.30 and draw all possible hydrochemical and hydrological conclusions. The data are from known municipal wells, but with no records on depth or casing conditions. Exercise 6.9: A well provided water from a sandstone aquifer underlain by clay that contained (in mg/l) Na: 20; Ca: 30; Mg: 3, Cl: 15; SO4: 19; and HCO3: 150. The well was deepened in order to increase the pumping yield and the new water contained (in mg/l) Na: 25; Ca: 60; Mg: 4; SO4: 15; and HCO3: 210. Is the increase in ion concentration, for example, doubling of the calcium concentration, alarming in any way?


Chapter 6

Fig. 6.29 Data (hypothetical) from six samples collected from a spring over 5 years (no units were mentioned in the original report).

Fig. 6.30 Fingerprint diagram of old municipal wells of which no records of depth and casing construction are available.

Chemical Parameters: Data Processing


Exercise 6.10: A spring emerges in alluvium, and its water composition is (in mg/l) K: 4; Na: 10; Ca: 42; Mg: 22; Cl: 2; SO4: 20; and HCO3: 220. Which rocks can be excluded as aquifer components? Exercise 6.11: Shallow water in a crystalline terrain has 200 mg Na/l and 450 mg Cl/l. What may be the origin of the water? Exercise 6.12: A well was terminated at a depth of 250 m in sedimentary rocks. The water abstracted had poor taste and was found to contain 450 mg SO4/l, balanced mainly by calcium. What does the composition indicate? What can be done to improve the water quality?


A good hydrochemical study is well planned in advance, and as little as possible is left to luck or fate. The rst stage is a clear denition of the goals or purpose of the study, its extent, and the means available. The answers will differ from one case to another, but there is a common thread: a thorough understanding of the water system under study has to be reached, and that in turn has to be based on high-quality data collected in the eld or obtained in laboratories. There is always a limit to the number of water sources, wells, and springs that can be included in a study, there is a limit to the number of periodically repeated measurements possible, and there is a limit to the type and number of laboratory analyses performed. Thus planning of hydrochemical studies is rmly anchored in optimization decisions. This chapter is devoted to these topics.

7.1 Representative Samples

The discussion may be opened with a problem. Temperature measurements conducted at a spring revealed 168 C at the edge of the water body, 188 C at the center at a depth of 5 cm, and 218 C at the center at the maximal depth, which was 1.3 m. Has the spring three temperatures? Is one value more representative than another? Or should we apply the average measured temperature? The measured temperatures differed substantially, and the cause of these differences has to be understood in order to select the right value. In this example it is clear that the spring water emerged at a certain temperature, but reequilibrium with the ambient air temperature occurred

Planning Hydrochemical Studies


near the surface. This leads to the conclusion that the temperature measured at the maximal depth is closest to the indigenous value. One may generalize: the temperature most different from the ambient air temperature is most representative, not the average value. One may go on to ask, where in this spring should a sample be collected for laboratory analyses. The temperature can be used as a guide for the location of spring water that has had minimal communication with the surface, that is, a minimum of evaporation, oxidation, or incorporation of surface materials. Thus the most representative sample of the spring is as deep as possible and as far as possible from the spring pool edges. Temperature measurements are a sensitive guide to the most representative spring sample, and they should be conducted rst, followed by sample collections and other in situ measurements (e.g., pH, dissolved oxygen, conductivity). Wells also have many facesa nonpumped well contains a column of water that has possibly interacted with its surroundings and reveals certain temperature values and a certain composition. Upon pumping, water that was shielded in the aquifer enters the well and the properties of the water in the well change. For this reason, water from pumped wells is in many cases regarded to be most representative of its aquifer water. Pumping should be continued until temperature, conductivity, and other parameters reach a constant value. By systematically lowering a temperature sensor into the water standing in a nonpumped well, a temperature prole can be obtained. Commonly the temperature near the water table is closer to the local ambient air temperature; deeper, a constant temperature is obtained that is representative of the aquifer. Occasionally, temperature increases with depth, and in rare cases temperature reversals may be observed, that is, a zone of lower-temperature water is overlain by a zone of highertemperature water. The latter case indicates lateral ow of the groundwater and differences in rock conductivity. If such a well is pumped in order to collect samples and conduct eld measurements, the values obtained will be a sort of average for the groundwater system being studied. In practice, various modes of sampling are applied: proles in nonpumped wells as well as samples in pumped wells. The mode of sample collection has to be taken into consideration at the data processing stage. Overpumping of a well may change the local pressure distribution in the water system to the extent that water from an adjacent aquifer may breach in and change the water properties. Thus overintensive pumping can introduce new complications. An obvious example is encroachment of seawater into coastal wells.


Chapter 7

The question of what represents water samples collected at wells has also to be addressed in light of well casing perforations. Well casings may be perforated along the entire section of the saturated zone, or they may be perforated only at certain intervals. Thus, a knowledge of the perforation geometry of a well is needed to understand what a collected sample represents. The discussion so far may create the impression that representative water samples are out of reach and nothing can be done about it. In fact, simple precautions provide reasonable solutions: The mode of data and sample collection in the eld has to be written down and taken into account at the data interpretation stage. Samples protected from surface interaction are preferable. In nonpumped wells, measuring of proles is recommended. In pumped wells, samples should be collected only after stabilization of properties has been achieved. The relevant pumping history has to be documented. Periodically repeated data collection is desirable. Conrmation of previous data indicates good representation of all data sets. Variations in the measurements call for careful sorting of the most representative values (which necessitates understanding of the causes of the observed variations).

7.2 Data Collection During Drilling

The ngerprint diagram shown in Fig. 7.1 depicts gradual salinization with depth at the Amiaz 1 well, west of the Dead Sea (Mazor et al., 1969). Fresh water was encountered at a depth of 32 m, whereas saline water of the local Tverya-Noit group was found at a depth of 85 m. A practical consequence of this is that some fresh water may be abstracted from a depth of 3040 m. The example of the Amiaz 1 well can be generalized: in each area several water bodies may be passed by a drill. All of them should be documented in the drillers records, all should be measured in situ, and samples should be collected for laboratory measurements. The study of water encountered during drilling causes technical difculties: most important is the possible interference of water introduced by the drilling procedure, difculties in noticing natural water horizons that are passed by the drill, and the cost of stopping the drilling operation for measurements. These difculties can be overcome in the following ways: . Use of every interruption in drilling (e.g., weekends or mechanical breakdowns) to measure the water table, temperature, and

Planning Hydrochemical Studies


Fig. 7.1 A ngerprint diagram of water from various depths collected during drilling of the Amiaz 1 well, west of the Dead Sea (Mazor et al., 1969). Several water horizons with different water qualities were encountered.

conductivity. Repetition of these measurements, during pauses in the drilling operation, may reveal progressive changes, indicating restoration of the water system. At each drilling pause, water samples should be collected for laboratory analyses. A sample of the water applied for the drilling should be analyzed as well. Differences between the latter and the well samples will indicate the water bodies encountered and their properties. Water in the drill hole should be removed with a bailer, that is, a water sampling rod, lowered and lifted with the drilling equipment. The amount of water removed should be several times the volume of the water-lled section of the drill hole. The bailer also serves to collect the samples. If the water is quickly transferred into bottles,


Chapter 7

. .

the temperature may even be measured in them. However, lowering a temperature logger, a pump, and a special sampling device into the drill hole is preferable. Whenever possible, dry drilling (with compressed air) is preferable. The budget allocated for drilling a well should include the costs of several stops required to measure water bodies that might be passed.

Information obtained during drilling is most valuable. Yet in many cases this information is not collected. Measurements during drilling provide the hydrological information in the depth axis. Therefore, it is essential that a hydrochemist performs detailed work during each drilling operation. Thus the planning of hydrochemical studies should routinely include follow-up of drilling operations.

7.3 Depth Proles

Figure 4.21 depicts temperature proles in a well close to the Mohawk River, New York. In May a temperature of 438 F is observed at the measured depth interval of 205165 ft above sea level. The July prole looked totally different: it showed 578 F at the top, 648 F at the center, and 528 F at the bottom. The January prole looks different again: 568 F at the top, 688 F at the center, and 528 F at the bottom. The interpretation of these temperature proles is discussed in section 4.8. For our present topic, the planning of hydrochemical studies, it is important to keep in mind that water strata are not necessarily uniformif they vary in their temperature proles, they may vary in other parameters as well. A sample collected from a pumping well provides average water properties and the detailed prole provides the ne structure, which is most important to the understanding of the dynamics of groundwater movement, as discussed in section 4.8. Depth proles in observation wells, or nonpumped wells, are conducted by lowering sensors into the well. The depth is usually read from markings on the electrical cable. The lowering of sensors into the well agitates the water and mixes the water column in the well. For this reason, . . . Measurements were taken downward so the sensor enters undisturbed parts of the water column in the well. Several parameters are measured together, for example, temperature, conductivity, and pH. Water level measurements, which may slightly agitate the water column, should be done last.

Planning Hydrochemical Studies


Samples can be collected from a depth prole by carefully lowering a cylindrical sampling bottle (commercially available). It should be gradually lowered to deeper sections so that each bottle collects undisturbed water. The depths of perforated sections, and other details of the well construction, must be known for proper interpretation of the data obtained in each prole. Planning of a hydrochemical study has to take into account the need to measure depth proles and to select the proper time to do them.

7.4 Data Collection During Pumping Tests

Section 4.6 is devoted to chemical and physical measurements during pumping tests. The conclusion reached is that physical and chemical followup of pumping tests is essential for their proper interpretation. Pumping of one water body (aquifer) is commonly assumed, but physical and chemical measurements can establish the number of water bodies affected by the pumping. Thus the hydrochemist should participate in pumping tests and in the interpretation of their data. The equipment needed includes probes for measuring conductivity and temperature, to be placed at the pump outlet to ensure minimal temperature reequilibration. Samples for dissolved ions, stable hydrogen and oxygen isotopes, and tritium measurements should be taken before pumping begins, or immediately at the beginning, and then at intervals up to the end of the pumping. About 10 samples should be taken: the intervals should be planned in light of the pumping test program. The rst and last samples should be sent to the laboratory rst. If they reveal the same concentrations, and provided the temperature and conductivity remained constant during pumping, then pumping of one water system is demonstrated. But if conductivity and/or temperature changed during pumping, or the rst and last sample were found to differ in their properties, then the rest of the samples should be sent for analysis. Modes of data interpretation are discussed in section 4.6.

7.5 Importance of Historical Data

The data collected during the drilling of the Amiaz 1 well (section 7.2 and Fig. 7.1) were put aside once the drill entered saline water and the well was abandoned. Several years later a water source of low output but good quality was needed in the area; on that occasion all historical data were scanned and studied. The existence of the required water body was spotted from the historical data, at no extra cost. A study of groundwater systems along a transect through the Judean Mountains, central Israel, was recently performed (Kroitoru, 1987; Kroitoru et al., 1987). Besides many new


Chapter 7

measurements, all available data from published reports and unpublished archives were incorporated. One measurement turned out to be of special value: postbomb tritium was observed in the Elisha Spring, situated on the eastern end of the Judean Desert, 22 km east of the recharge area, which is near Jerusalem. The point of importance was that the tritium was observed as early as 1968, at most 15 years after the onset of nuclear bomb tests, held between 1953 and 1963. Thus it turned out that groundwater ow to the Elisha Spring was at least 22:15 1.5 km/year, which in turn indicated ow in karstic (old) conduits. The historical data provided much additional information in this study and turned out to be most useful (Kroitoru, 1987). Many researchers tend to disregard data obtained by previous workers and prefer to concentrate on their own new measurements. Explanations given are that the old data are incomplete, the laboratories were not as good in the old days, or the old data are not available. These arguments may easily be countered: . . . . Many of the previous researchers produced excellent data, and the quality of the old data can be assessed by use of the processing techniques discussed in section 5.10. Historical data are available from local water authorities, data banks, and professional publications. Historical data have the advantage of being available free of charge. The old data are available at the early stages of a new study and can help in planning the new research campaign.

It is assumed that the reader is now convinced that historical data are useful. But the most important argument has not yet been spelled out: the old data were collected when the water systems were less disturbed by human activity. Thus historical data recorded information that cannot now be collected and serve as a database needed to understand the evolution and dynamics of studied water systems. Historical data also enlarge the time span of repeated observations, the topic of the next section.

7.6 Repeated Observations, or Time-Data Series

Repetition of eld measurements and laboratory analyses is an essential part of hydrochemical studies. Sources of recharge vary over the yearsummer rains, winter rains, and snowmelt. These are distinguishable by their isotopic (and occasionally also chemical) composition (Chapter 9), and their seasonal inputs can be established provided the relevant water systems are monitored over at least 1 year. Water table and discharge responses to precipitation or ood events provide information on hydraulic interconnec-

Planning Hydrochemical Studies


tions. Such responses can be detected only by comparing the results of repeated observations. Chemical variations and temperature uctuations are indicative of mixing processes, thus justifying the effort invested in repeated observations. Last, but not least, man-induced changes in water systems can be understood by comparing data from repeated measurements. These provide indications of deterioration caused by harmful human impacts, or of improvements achieved by proper management. Having praised repeated measurements, we now discuss their incorporation into the planning of hydrochemical studies. A common rule of the thumb is that each water source should be studied four times to cover at least one hydrological cycle, including the four major seasons. This may be regarded as a minimum, because time-data series with only four points suffer from poor resolution. Many data pointsmany repetitionswere needed in the hydrographs of the wells depicted in Figs. 4.74.10, the temperature observations plotted in Figs. 4.194.23, and the discharge, temperature, and chlorine concentration values discussed in the time series of Figs. 4.244.27. Thus in many studies monthly measurements are needed for at least 14 consecutive months in order to fully cover a hydrological year. Repeated studies are especially necessary in areas that have few accessible wells or springs. When working on single water sources, multisampling provides an insight into the underground plumbing, establishing the existence of a single-water aquifer, several waters that intermix (sections 6.46.6), or conduit-dominated versus porous medium recharge intake (sections 2.2 and 2.9). Thus measurements may have to be reported once in every few years (Fig. 6.22), seasonally, monthly, daily (Fig. 6.21), or hourly (pumping tests). In the absence of repeated measurements the dynamics of a system may be revealed by measurements performed on many sources (wells or springs) in the studied area.

7.7 Search for Meaningful Parameters

Let us have a look at the compositional diagrams of the Combioula Spring study (Fig. 6.26). Suppose a new study is planned to establish the impact of new wells on the warm mineral springs, and suppose that for budgetary reasons the new study has to be based on repeated measurements of only a few parameters. The detailed study portrayed in Fig. 6.26 revealed that the dominant process in the Combioula Spring complex is intermixing of warm saline water with cold relatively fresh water. The parameters to be included in the new study should be reliable tracers of the mixing. Thus, they have to be selected from the parameters that provide good mixing lines in Fig. 6.26, namely, Li, Na, K, Cl, and temperature. Parameters that have equal values


Chapter 7

in both end members are redundant (these include in our example Ca, Sr, HCO3, and SO4). Parameters revealing large data spreads are useful. By this method of sorting of parameter efciencies we are left in the Combioula case with ve parameters: Li, Na, K, Cl, and temperature. Temperature, being a physical parameter (with short memory, as it readily reequilibrates), should be included among the most meaningful parameters. The remaining parameters should include at least one anionchlorineand one cation, perhaps sodium, which is dominant and easy to measure. The selection of meaningful parameters is essential for economic reasons, focusing efforts and means on a smaller number of selected, more promising, parameters. The search for meaningful parameters necessitates that each study has a preliminary stage, at which a large number of parameters are measured. From the preliminary results the most informative parameters are then selected. This rst stage of measuring a large number of parameters is essential, as no case study resembles previous ones, and the list of meaningful parameters varies from case to case: temperature measurements are essential in warm water systems and less informative in cold systems with constant temperatures; chlorine is less important in many fresh water systems, but essential to trace brines; in contrast, HCO3 is a sensitive tracer in fresh waters. Stable isotope measurements are meaningful in aspects that are different from the meaning of dissolved ions (e.g., altitude of recharge, identifying evaporation brines, or indicating a thermal history). Hence, if money is tight, the list of dissolved ions measured may be cut in order to save the stable isotopes. Tritium is an essential age indicator for post-1953 water, but it can be dropped if preliminary work reveals that the study deals with older water. Carbon-14 measurements necessitate handling of hundreds of liters of each sample, or payment of a higher price for accelerator determinations. Therefore, although they are a must in the preliminary study stage, they may be reduced once the basic conceptual model is reached. The preceding sentence provides a guideline to the timing at which the number of parameters measured in a study can be cut: when an initial conceptual model is reached. Fewer parameters have to be measured to check the validity of the model or to follow the evolution of a system due to exploitation.

7.8 Sampling for Contour Maps

Extensive hydrological studies, extending over large areas and with large numbers of accessible wells, pose severe difculties in presenting and processing the wealth of data obtained. One mode is to produce maps with contour lines of the various parameters.

Planning Hydrochemical Studies


Planning of a hydrochemical study should include the question, will the data be expressed in contour maps? If so, data have to be obtained with an adequate geographical coverage and adequate density of measured points. These requirements are necessary to ensure adequate resolution and to avoid white holes in the maps. Hydrochemical contour maps should be prepared from data collected at the same time. Mixing of data from different seasons, or even different years, reduces the meaning of the map. On the other hand, comparison of contour maps of data obtained at different times may be most informative. The need for many sampling points may result in a need to cut other efforts, for example, to reduce the number of measured parameters, as discussed in the previous section.

7.9 Sampling Along Transects

Sampling at wells and springs lying along a selected transect facilitates data processing and presentation. An example from a recent study in the Judean Mountains is given in Fig. 11.17. A hydrochemical transect has the advantage of graphically linking parametric variations with geographical locations (topographic transect), geological features (geological transect), and hydrological setting (water table transect), as seen in Figs. 4.5 and 4.6. Planning a hydrochemical study should include the question of whether the transect approach is desired. If so, the locations of the transect should be decided. Such a decision should take into account . . . . The geological structures (a transect crossing major structures is desired) Availability of accessible wells and springs Priority to wells and springs of large discharge (best representing the studied water system) Even distribution of sampling points along the transect

7.10 Reconnaissance Studies

The term reconnaissance study relates to studies conducted for the rst time, covering extended areas, to be completed fast and with minimal costs. The purpose of reconnaissance studies is to get a general picture of the water systems involved, to locate promising sites where large amounts of highquality water can be found, to scan the area for features of special interest, to locate possible pollution processes, and to arrive at a conceptual model. The results of reconnaissance studies are the basis for the planning of


Chapter 7

detailed studies in selected areas. The major points characterizing reconnaissance studies are the inclusion of the maximum available number of wells and springs and the measurement of as many parameters as possible. The rst point is needed for representative samples; the second point is necessary in order to nd those parameters that are most informative in each studied system. In planning a hydrochemical study, a clear distinction has to be made between a reconnaissance study and a detailed study.

7.11 Detailed Studies

A detailed study is characterized by . . . . . Relatively small study areas Existence of former datahistorical or of a preliminary study Requirements for thorough research that should provide answers to specic questions A quantitative approach, whenever possible Inclusion of observations needed to check a proposed conceptual model

Detailed studies are conducted over a period of a year or more and include adequate repetitions of eld measurements and sample collections for laboratory analyses. These studies are based on a variety of sampling strategies, for example, repeated sampling in springs and wells, depth proles in nonpumped wells, search for water occurrences during drilling, and measurements during pumping tests. The number of parameters measured will be large at the beginning of a detailed study, but the number will gradually shrink as the system is better understood and the most informative parameters are spotted.

7.12 Pollution-Related Studies

Pollution is part of contemporary hydrology, a topic discussed in Chapter 16. Let us stress here only that pollution-related studies may address a specic environmental problem and/or apply contaminants as tracers to understand ow paths in the natural system. The pollution-related aspect has a bearing on the planning stages of a study. The following information has to be collected rst: . An inventory of potential pollution sources that may affect groundwater in the studied region (e.g., factories, sewage facilities, agricultural activity).

Planning Hydrochemical Studies


. . . . . . .

For each potential pollution source specic information is desired, for example, date of beginning of the activity, type of contaminants, mode of release, periodicity of release, and quantities. Historical data of water composition in the region in general and in selected study wells in particular, in order to assess the base data pertaining to prepollution times. Other information needed for any hydrochemical study, discussed in the previous sections. Complaints by local groundwater consumers.

The next stages are to Formulate the research problems to be addressedscientic and applied Decide on the nature of the studyreconnaissance or detailed Select monitoring pointswells or springs situated near all potential pollution sources (in the downow direction), surface water bodies (rivers, lakes, operational ponds, etc.), and water supplying wells Decide upon parameters to be measured, bearing in mind the specic pollutants already noticed in the groundwater or expected from known potential polluters Plan the monitoring frequency of the various parameters Locate the laboratories that will analyze the dissolved ions, gases, and specic pollutants, and get from them detailed water sampling instructions

. . .

7.13 Summary: A Planning List

It is said that a well-formulated question contains half the answer. By the same token, a well-planned study is the key to the success of the study. The following list of planning stages is suggested and is given as a summary of the present chapter: 1. Dene the purpose of the studypractical and scientic. 2. Dene the study area. 3. Collect all available data (geographical, hydrological, geological, temperatures, chemical and isotopic compositions, time variations, and so on). 4. Develop a conceptual model, or several possible models, suggested by previous and new workers, based on the available data. 5. Dene the nature of the studyreconnaissance or detailed.


Chapter 7

6. Develop a sampling strategysampling for a contour map or sampling along a transect. 7. Prepare a list of wells, springs, and surface water bodies to be included in the study (in light of points 16). The total number of sampling points should be estimated. 8. List the locations for special measurements and sample collections (e.g., depth proles, sampling during drilling and during pumping tests). 9. List the parameters to be measured in the eld and the type of instruments needed. 10. List the parameters to be analyzed in laboratories, including the names of the laboratories and the types of sampling vessels needed. 11. Decide on the frequency of planned repetitions of eld measurements and laboratory analyses. 12. Consider potential bottlenecks that need special care, for example, access to wells on private property, long waiting time in a special laboratory, or cooperation of drilling authorities. 13. Develop a schedule and timetable. 14. Consider budget requirements, based on the above points and ordered by nature of expenditure: salaries, means of transportation, equipment, sample collection vessels, laboratory fees, maps and photos, miscellaneous items.

7.14 Summary Exercises

Exercise 7.1: Acquaint yourself with the research reported from the Saratoga National Historic Park, New York, as presented in Fig. 4.8 and the accompanying text. Discuss it in terms of planning such a study: What was the aim of the study? What is specic about the selected well site? Which type of parameters had to be measured? Exercise 7.2: You are asked to conduct a study of a spa. The manager brings you bottles with samples he has collected at three of his bathing installations. What will you do rst? Exercise 7.3: You are planning a study in an area that has a large number of wells marked on the map. How will you select the best wells for your study?

Planning Hydrochemical Studies


Exercise 7.4: What do you expect to nd in the drillers reports? Is it worthwhile to make the effort to get them for all wells you are going to investigate? Exercise 7.5: Does it matter whether a well is operated at the time of your arrival for its monitoring, or do you prefer to monitor a well that is constantly pumped before your arrival? Exercise 7.6: How will the planning of a study be inuenced by the fact that available wells and springs are very scarce?


8.1 Field Measurements

Certain chemical and related physical parameters have to be measured at the well or spring site. The list of parameters for eld measurements includes those that change in stored samples and cannot be measured in the laboratory in a meaningful way. Most conspicuous in this respect is temperature, but pH, alkalinity, and dissolved O2 and H2S may also change between sampling and analyses in the laboratory. There are many high-quality instruments available for measuring various parameters. These are accompanied by instruction manuals describing the operation of the sensors and calibration and measurement procedures. Portable versions are available for measuring parameters of water from springs or pumped from wells. Instruments for well logging (depth proles) are available with long cables, in versions suitable for surveys and in xed modes appropriate for continuous monitoring. Instrument sets are available that measure several parameters simultaneously, a procedure that is time saving and convenient. A comprehensive and easy to follow text on sampling procedures and biological, chemical, and physical measurements in the eld has been prepared by Hutton (1983). Field measurement instruments should be checked for their limits of detection, accuracy, and reproducibility, and their measurement errors should be established. This can be done with standards, duplicate samples, and dilution of samples, similar to the checks discussed for laboratory measurements (section 5.9). Such checks should be performed in preparation for eld work, and the results should be recorded and reported with the

Chemical Parameters: Field Work


data (sections 5.7 and 5.8). Checking the eld equipment in advance is essential to secure proper operation in the eld. Field measurements are needed for a number of purposes: Measurement of parameters that change, or may change, after removal of the water from the sampling point. Providing immediate information on water quality, needed to decide the extent of sample collection. Providing checks on the laboratory data. For example, disagreement between electrical conductance measured in the eld and TDI determined in the laboratory indicates erroneous eld measurements, bad handling of the samples on the way to the laboratory, erroneous laboratory results, or mislabeling of samples. Agreement between eld and laboratory data raises the condence in the data and indicates that no secondary processes have occurred between sampling and laboratory measurement.

8.2 Smell and Taste

On approaching a water source one occasionally senses an unpleasant smell. In most cases this is caused by sulfur compounds, mainly H2S. This information should be recorded in the eld notes and taken into account during data interpretation because the presence of H2S and related compounds indicates reducing conditions, bacterial activity, or possible occurrence of sewage or other pollutants. Human ability to smell H2S is limited to the parts per million range. At higher concentrations the odor is not noticed. Hence, if an H2S smell is noticed when approaching the site, but it disappears at the well or spring itself, a high H2S concentration should be suspected and relevant sampling is recommended. Smell is a crucial factor in the ranking of water quality. In some cases aeration of water is practiced in order to get rid of compounds causing unpleasant smells. Tasting of water provides immediate quality information, for example, . . . Estimate of the total salinity Identication of major ionsNaCl tastes salty, MgSO4 tastes bitter, and iron catches the mouth in an unpleasant way Identication of pollutants such as sewage or industrial waste

Tasting ability can be developed by tasting waters of known compositions. The information gained by tasting is of immediate use in


Chapter 8

the eld: different water types can be recognized, and more detailed sampling may be chosen for special cases. A word of warning is needed at this point: do not taste water if you suspect it to be contaminated.

8.3 Temperature
Potential uses of temperature data have been discussed in sections 4.74.9. The ease with which temperature is measured and the benets to the understanding of groundwater systems make the measurement of this parameter a must in every study. This is also true for repeated measurements, depth proles, and pumping tests. Temperature can be measured with mercury-lled thermometers or by thermistors. Resolution and accuracy of + 0.18 C are desirable. Thermometers should be calibrated by comparison with standard thermometers, or by immersing in fresh water and ice mixtures (08 C) and in fresh boiling water (the local boiling point is altitude dependent). Temperature data are needed for waterrock equilibrium calculations as well as for the identication of water groups, the determination of water end member properties (section 6.7), and to deduce the depth of water circulation (section 4.7).

8.4 Electrical Conductance

An electrical current can be carried through water by the dissolved ions. Electrical conductance is expressed in units of microohm/cm, also called microsiemens (mS). A positive correlation is observed between the electrical conductance and the TDI, expressed in meq/l. This correlation is linear up to 50 meq/l of TDI. At higher concentrations of dissolved ions the line in a conductanceTDI diagram levels off. The electrical conductance of a given water solution increases with temperature. Field probes of electrical conductance are therefore temperature compensated. Conductivity values obtained in the eld should be plotted against the corresponding TDI concentrations measured in the laboratory. A good linear correlation conrms the high quality of the data. Outstanding values should be suspected as erroneous and should be discussed with the laboratory staff for possible detection of errors or repetition of measurements. Conductivity measurements are of special use in the following cases: . Monitoring pumping tests for the detection of possible intrusion of different types of water (section 4.6).

Chemical Parameters: Field Work


. . . .

Measuring depth proles in nonpumped wells to search for different water strata (section 7.3). Monitoring water owing from a well opened just before sample collection: samples can be collected once a constant conductivity value is obtained. Continuous monitoring in observation wells to detect the arrival of rain and ood recharge. To substitute for TDI concentrations that are needed for data processing but are occasionally missing in cases of incomplete laboratory analyses. The needed TDI value may be read from the conductivityTDI curve of the studied system.

8.5 pH
The pH of a solution indicates the effective concentration of hydrogen ions, H. The units of pH are the negative logarithm of hydrogen ion concentration, expressed in moles per liter: pH log H The pH describes the composition of water: pH 7 indicates neutral water, lower values indicate acid water, and higher values indicate basic water. The pH is determined by means of a glass hydrogen ion electrode of known potential. Calibration is carried out with special solutions of known pH. The pH is controlled by various reactions and the presence of different compounds. In fresh water systems the carbonate system 2HCO32 2CO3 plays a primary role in determining the pH. In other CO22 cases the presence of H2S or its oxidized form, sulfuric acid, determines low pH. The pH value is an important parameter in water quality assessment in relation to corrosion problems and taste. A knowledge of the pH, up to + 0.1 unit, is essential for waterrock equilibrium calculations. Experts may be consulted for such calculations, but accurate pH data may be supplied by the eld hydrochemist. The pH measured in the eld should be compared to the pH measured in the laboratory. Agreement between the two values indicates that no related secondary reactions have occurred in the sample bottle, for example, loss of CO2 or biological activity. Whenever the two pH measurements agree, the water chemistry measured in the laboratory is relevant to the water in situ. However, deviations of the laboratory pH from the pH measured in the eld indicate either that one of the measurements is wrong, or that secondary reactions have occurred in the time elapsed since the


Chapter 8

samples were collected. In such cases the preservation of the sample has to be checked and improved (section 8.10), and the period between sampling and laboratory measurements has to be shortened. Disagreement between eld and laboratory pH measurements places a question mark over the reported concentration of biologically involved ions such as HCO3, NH4, SO4, H2, and Ca. At the same time, the reported concentrations of more conservative ionsCl, Br, Na, K, or Limay be correct.

8.6 Dissolved Oxygen

Rain and surface waters equilibrate with air, becoming saturated with dissolved oxygen. Equilibration with soil air goes on until water reaches the saturated zone, where it is isolated from further contact with air. The concentration of dissolved oxygen in air-saturated water depends on . . . Pressure, which is controlled by the altitude Temperatureincreasing the temperature decreases the oxygen solubility Salinityincreasing the salinity decreases the oxygen solubility (negligible for fresh waters)

The initial concentration of dissolved oxygen in recharged water can be computed for each study area. The concentration at sea level (1 atmosphere), as a function of the average annual local temperature, can be read from Fig. 8.1. At locations with altitudes above or below sea level, a correction factor has to be applied to the oxygen concentration read from Fig. 8.1. The altitude correction factors are given in Fig. 13.2. For example, air-saturated water at sea level at 178 C contains 9.0 mgO2/l and at an altitude of 330 m it contains 9.0 6 0.96 8.6 mgO2/l. Comparison of the calculated initial O2 concentration with the value measured in the eld reveals the fraction retained. The missing O2 has been consumed by oxidation of rocks and biological activity. The rate of oxygen consumption depends on the aquifer lithologythe occurrence of pyrite and other oxygen-consuming minerals, and the availability of organic compounds and nutrients needed for O2-consuming biological activity. The consumption of dissolved O2 serves also as a semiquantitative age indicator: older water tends to have lost most or all of its dissolved oxygen. Generally speaking, in phreatic aquifers water retains a signicant portion of the initial O2, whereas in conned aquifers little or no O2 is retained. Pollution by sewage and other organic compounds results in consumption of the dissolved oxygen.

Chemical Parameters: Field Work


Fig. 8.1 Dissolved oxygen (mg/l) in fresh water as a function of the ambient temperature.

Determining the amount of dissolved O2 is, thus, informative in several respects: . . . Dening the aquifer environment in terms of degree of anaerobic conditions. Detecting changes occurring in a water system: decrease in dissolved O2 may indicate an increase in biological activity connected to the arrival of sewage or other polluting uids. Identifying systems with dominant conduit-controlled recharge and underground ow. These have limited waterrock contact and fast ow, and retain their initial dissolved O2 even at long distances from the intake zone. Identifying conned systems of old water, which are likely to have lost their O2. Identifying intrusion of water from adjacent wells as a result of pumping tests and in intensively exploited well elds. Identifying different water strata in depth proles. Identifying mixing of different water types by the occurrence of forbidden ion combinations, for example, dissolved O2 and H2S.

. . . .

The concentration of dissolved oxygen is determined by two electrodes immersed in an electrolyte contained in a vessel with an oxygen-permeable membrane wall. The cell is placed in a container through which the measured water ows. Oxygen diffuses into the cell in direct proportion to its concentration in the measured water. The diffused oxygen is consumed


Chapter 8

by the cathode, creating a measurable current that is proportional to the diffused oxygen and, in turn, to the O2 concentration in the measured water. Instruments measuring dissolved O2 are calibrated by immersion in aerated water samples, for which the dissolved O2 is computed from given curves that take into account the water temperature and salinity, as well as the altitude.

8.7 Alkalinity
Alkalinity is related to the sum of the carbon-containing species dissolved in the water: CO2, HCO3, and CO3. Bicarbonate is commonly the dominant ion. Alkalinity has to be measured in the eld because CO2 is often pressurized in groundwater (due to addition of CO2 from soil and other underground sources). Upon exposure to the atmosphere some CO2 may leave the water, causing part of the HCO3 to break down. For these reasons it is highly recommended that alkalinity be determined in the eld. Fieldmeasured alkalinity values are needed for waterrock saturation calculations. Various setups are available for alkalinity measurements in the eld by titration of the sample with an acid and pH coloring indicator.

8.8 Sampling for Dissolved Ion Analyses

Sampling procedures for determining the amounts of dissolved ions should be discussed with the relevant laboratory. Commonly, half-liter plastic bottles are adequate. Occasionally a separate bottle is needed, to which a few drops of pure acid are added to secure low pH in order to prevent precipitation of some ions, such as carbonates. For SiO2 analyses, addition of known amounts of distilled water is recommended to avoid precipitation of silica as a result of cooling of the water. Separate samples are commonly collected for H2S determination. To these a xative agent is added, each laboratory preferring its own material. The details of a sampling expedition have to be worked out with the laboratory staff in advance, and the proper (clean) bottles have to be obtained. In addition to being clean, bottles should be rinsed in the sampled water before taking samples. Always label the samples in the eldnever rely on your memory and make sure the labels are complete.

Chemical Parameters: Field Work


8.8.1 Filtering
Water samples contain dispersed soil particles and colloids. These can be removed by ltration, either in the eld or in the laboratory. Some workers carefully lter every sample in the eld; others argue that the water emerges with particles that are part of the hydrological system under study and therefore their ltration can be postponed until arrival at the laboratory or skipped altogether. Filtering requires experience: nonexperienced personnel may introduce contamination and cause fractionation. The topic should be discussed with the laboratories concerned.

8.9 Sampling for Isotopic Measurements

The nature of isotopic data is discussed in later chapters, but sample collection techniques are discussed here.

8.9.1 dD and d18O Measurements

Fifty-milliliter samples are adequate. Evaporation of samples has to be avoided by prompt closing of the bottles and storage in the shade. Normally each laboratory prefers its own bottles.

8.9.2 Tritium
One-liter bottles are desirable to allow for repeated measurements and preconcentration (in the case of low tritium concentrations). Glass bottles are preferred, as tritium can diffuse through PVC bottles and equilibrate with the air.

8.9.3 Carbon-14
Fifty- to two-hundred-liter samples are needed (according to the HCO3 concentration and the laboratory requirements). These may be collected in large containers with minimum exposure to air. The detailed procedure should be discussed with the laboratory. Samples have to be delivered to the laboratory within days to avoid equilibration with air. Precipitation of the dissolved carbon species and their extraction from 50200 1 is preferably done in the eld. This procedure requires experience (guided by the laboratory staff or, preferably, carried out by a trained hydrochemist). Precipitation in the eld is time consuming, but it reduces the volume and weight of samples that have to be transported to the laboratory.


Chapter 8

For 14C acceleratormass spectrometer analyses, 1-1 samples are usually enough, but details should be discussed with the laboratory staff.

8.9.4 Carbon-13
Three-liter samples may be needed, or precipitation and extraction may be done in the eld, similar to the treatment of the 14C samples. Separate bottles are needed for 13C, as the treatment of the large samples for 14C may introduce signicant fractionation in the 13C value.

8.9.5 Noble Gases

Samples are collected in glass tubes with special stopcocks or in copper tubes with special clamps. The main concern is absolute avoidance of air contamination. This aspect is further discussed in Chapter 13 and should always be coordinated with the laboratory personnel.

8.10 Preservation of Samples

The storage of samples during transport from the eld to the laboratory, and on the laboratory shelf, has to be done with care and expertise. Major points are . . . Keep the samples cold. Samples left for several hours in the sun after sampling or samples left in a hot car for several days may be spoiled by secondary reactions. Keep the samples in the dark. Place them in boxes or store them in dark rooms. Exposure to light enhances biological activity. In order to avoid biological activity, samples are occasionally poisoned by adding chemicals containing ions that will not be measured in the laboratory. Mercury iodide is a convenient preservation substance. It is available as small orange crystals; a single small crystal added to a bottle of water is adequate. Addition of a preservative to a sample should be clearly marked on the bottle. Normally, each laboratory advocates a specic preservative.

8.11 Eforescences
Small crystals of salts are occasionally seen to cover the soil and rocks near springs and seepages. In arid regions such eforescences, or salt crusts, are also seen on soils in areas detached from springs or other types of surface water.

Chemical Parameters: Field Work


Eforescences are formed by evaporation of rain or spring water leaving behind dissolved salts. Inltrating rainwater redissolves such eforescences, salinizing local groundwater. The composition of eforescences is therefore of interest with regard to the hydrochemistry of the water they precipitated from and with regard to the groundwater they salinize. Tasting of eforescences can provide immediate clues as to their composition: white material with a salty taste is halite (NaCl); white insoluble material with no taste is most likely gypsum (CaSO4 ? 2H2 O); white material that readily dissolves with a bitter taste may be epsomite (MgSO4 ? 7H2O), and white material that readily dissolves with no taste but a sense of cooling is most likely nitrate (KNO3 or NaNO3). The occurrence of eforescences should be documented in the eld notebook. Samples, in plastic or glass containers, should be sent to the laboratory for chemical analysis. Conceptual models developed for water systems should incorporate the occurrence of eforescences of observed compositions.

8.12 Equipment List for Field Work

A great deal of equipment is needed for hydrochemical eldwork. The details vary according to the specic nature of each expedition, but experience shows that going over an equipment list is always benecial. The following items of equipment will be required: 1. Sampling schedule (Chapter 7), maps, and writing material. 2. Field measuring equipment for temperature, conductivity, pH, dissolved oxygen, and alkalinity. Specic materials are needed for these instruments for calibration and rinsing. Also carry extra batteries and other parts. 3. Sample collection bottles. These have to be prepared carefully so that (1) all the required varieties are included, (2) all bottles are clean (even new ones have to be cleaned), and (3) the bottles are all well packed in boxesthese will be needed for the lled sample bottles. 4. Filtering equipment (if ltering is to be carried out). 5. Precipitation equipment for 14C and 13C (if precipitation is to be done in the eld). 6. Labeling material (labels or inks that have been tested to remain on the relevant bottles). Note: Proper eld measurements and well-collected samples rapidly delivered to the laboratories are the key to high-quality data. These are, in turn, the key to high-quality hydrochemical studies.


~~~~~~~~ Repeated Sampling and Measuring

at different seasons or pumping rates are necessary to

Understand the Dynamics of Studied Systems ~~~~~~~~


9.1 Isotopic Composition of Water Molecules

The denitions of elements and isotopes were presented in sections 5.1 and 5.2. Elements are dened by the number of protons in the nucleus of their atoms. Hydrogen has one proton and oxygen has eight protons. Isotopes are dened as variations of a given element, differing from each other by the number of neutrons. As presented in section 5.2, the hydrogen isotopes are
1 2

Hcommon hydrogen; 1 proton Hdeuterium (also written D); 1 proton 1 neutron 3 Htritium (also written T); 1 proton 2 neutrons Tritium is radioactive and will be discussed in Chapter 10; common hydrogen and deuterium are stable. Oxygen has the following isotopes: Ocommon oxygen; 8 protons 8 neutrons Oheavy (very rare) oxygen; 8 protons 9 neutrons 18 Oheavy oxygen; 8 protons 10 neutrons
16 17

Water is composed of hydrogen and oxygen, so it occurs with different isotopic combinations in its molecules. Most common and of interest to hydrochemists are 1H2 16O (common), 1HD 16O (rare), and 1H2 18O (rare). The water molecules may be divided into light molecules (1H2 16O) and heavy water molecules (1HD 16O and 1H2 18O).


Chapter 9

9.2 Units of Isotopic Composition of Water

The isotopic composition of water is expressed in comparison to the isotopic composition of ocean water. For this purpose an internationally agreed upon sample of ocean water has been selected, called Standard Mean Ocean Water (SMOW) (Craig, 1961a, 1961b). The isotopic composition of water, determined by mass spectrometry, is expressed in per mil % deviations from the SMOW standard. These deviations are written dD for the deuterium, and d18O for 18O: dD% and d18 O% 18 O=16 Osample 18 O=16 OSMOW 18 O=16 OSMOW 61000 D=Hsample D=HSMOW 61000 D=HSMOW

Water with less deuterium than SMOW has a negative dD; water with more deuterium than SMOW has a positive dD. The same is true for d18O.

9.3 Isotopic Fractionation During Evaporation and Some Hydrological Applications

Evaporation is a physical process in which energy-loaded water molecules move from the water phase into the vapor phase. Isotopically light water molecules evaporate more efciently than the heavy ones. As a result, an isotopic fractionation occurs at partial evaporation of water: the vapor is enriched in light water molecules, reected in relatively negative dD and d18O values. In contrast, the residual water phase becomes relatively enriched in the heavy isotopes, reected in more positive dD and d18O values. The isotopic separation, or fractionation, is more efcient if the produced vapor is constantly removed, as for example by wind blowing away vapors produced above an evaporating pond. Figure 9.1 presents the composition of water samples successively collected at a pond in Qatar (Yurtsever and Payne, 1979). The composition of the samples is plotted on a dDd18O diagram. A progressive enrichment in the heavy isotopes is noticed, indicating that the residual water in the pond was progressively enriched in dD and d18O as the isotopically light vapor was removed. The original water had a composition of dD 0% and d18O 1.4%, and the last sample reached values of dD 33% and d18O 5.6%. The line connecting the sample points is called the evaporation line, and its slope is determined primarily by the prevailing temperature and air humidity.

Stable Hydrogen and Oxygen Isotopes


Fig. 9.1 Isotopic composition of water samples successively collected at an evaporating pond at Qatar. The water in the pond became progressively heavier in its composition. (From Yurtsever and Payne, 1979.)

In surface water bodies that evaporate to a very great extent, the isotopic enrichment ceases or is even reversed. However, except in very rare cases, natural water bodies, such as lakes or rivers, are only partially evaporated in the range in which isotopic enrichment of the residual water occurs. Isotopic fractionation during evaporation causes fractionation during cloud formation: the vapor in the clouds has a lighter isotopic composition than the ocean that supplied the water. Upon condensation from the cloud, during rainformation, the reverse is true: the heavy water molecules condense more efciently, leaving the cloud residual vapor depleted of deuterium and 18O. Residual evaporation water is thus tagged by high dD and dD18O values, an observation used to trace mixing of evaporation brines with local fresh water. An example of two mineral springs located on the Dead Sea shore is given in Fig. 9.2. The Hamei Zohar and Hamei Yesha springs are seen to lie on a fresh waterDead Sea mixing line, indicating that these springs contain recycled Dead Sea water brought to the surface with the emerging fresh water recharged at the Judean Mountains (Gat et al., 1969). From the information included in Fig. 9.2, one can calculate the percentage of Dead Sea brine intermixed in the Hamei Yesha and the Hamei Zohar springs. At Orapa, northern Botswana, a new well eld of conned water was developed and two hypotheses were proposed to explain the origin of


Chapter 9

Fig. 9.2 Stable hydrogen and oxygen isotopic composition of the Hamei Zohar and Hamei Yesha mineral springs, Dead Sea shores. The linear correlation indicates that the springs water is formed by intermixing of Dead Sea brine with local fresh water. (From Gat et al., 1969.)

recharge: either underground ow of recharge water from lakes and rivers 45 km distant, or local rain. The consultants of the local diamond mine ruled out local recharge and favored replenishment from the lakes. Results of an isotopic composition survey, depicted in Fig. 9.3, show the dD and dD18O values of the groundwater in the wells, the average annual rain composition in neighboring meteorological stations, and the lakes and rivers mentioned.

Fig. 9.3 Isotopic data of conned groundwater at Orapa, Botswana (s), average annual rain in neighboring meteorological stations (letters), and 45-km-distant lakes (D) and rivers (x). (From Mazor et al., 1977.)

Stable Hydrogen and Oxygen Isotopes


The dD and d18O values of the groundwater in the wells were observed to be signicantly lighter (more negative) than in the lake and river waters, which were enriched in the heavy isotopes due to intensive evaporation losses. Thus the hypothesis of recharge from the lakes could be ruled out, and recharge by local rain was supported. However, a slight but analytically signicant difference can be seen between the composition of average annual rain and local groundwater. This was explained by an observation that only intensive rains are effectively recharging the groundwater, and these were observed by Vogel and Van Urk (1975) to have an isotopic composition that is lighter than average annual rain composition (the amount effect, section 9.6).

9.4 The Meteoric Isotope Line

Harmon Craig published (1961a) a dD and d18O diagram, based on about 400 water samples of rivers, lakes, and precipitation from various countries (Fig. 9.4). An impressive lining of the data along the best-t line of dD d18 O 10 has been obtained. Outside this line plot data from East African lakes that undergo signicant isotopic fractionation due to intensive evaporation losses.

Fig. 9.4 Isotopic data of about 400 samples of rivers, lakes, and precipitation from various parts of the world. The best-t line was termed the meteoric line. Its equation, as found by Craig (1961a), is dD 8d18 O 10. The data in the encircled zone of closed basins is for East African lakes with intensive evaporation.


Chapter 9

The data in Fig. 9.4 lie on a straight line in spite of the very wide range of values: dD of 300% to 50%, and d18O of 42% to 6%. This line, called the meteoric line, has been found, with some local variations, to be valid over large parts of the world. The meteoric line is a convenient reference line for the understanding and tracing of local groundwater origins and movements. Hence, in each hydrochemical investigation the local meteoric line has to be established from samples of individual rain events or monthly means of precipitation. A specic example of a local meteoric line, from northeastern Brazil, is given in Fig. 9.5. A local meteoric line is obtained: dD 6.4 d18O 5.5 (Salati et al., 1980). Examples of equations of local meteoric lines reported from various parts of the world are given in Table 9.1. The composition of precipitation is reected, directly or modied, in the composition of groundwater. Common practice is to plot groundwater data on dD d18O diagrams, along with the meteoric line of local precipitation as a reference line. Examples are given in Figs. 9.69.8. In Fig. 9.6 the composition of the groundwater plots are close to the local meteoric line, ruling out secondary processes, such as evaporation prior to inltration or isotope exchange with aquifer rocks. In Fig. 9.7 the groundwater data fall distinctly below the relevant meteoric line, indicating that secondary fractionation has occurred, or that the waters are ancient and were recharged in a different climatic regime that

Fig. 9.5 Isotopic composition of precipitation in the Pajeu River basin, Brazil: s, months with rain over 50 mm/month; ., months with lower precipitation amounts. A local meteoric line is obtained with the equation dD 6:4d18 O 5:5. (From Salati et al., 1980.)

Stable Hydrogen and Oxygen Isotopes Table 9.1 Examples of Regional Meteoric Lines Region Global meteoric line Northern hemisphere, continental Mediterranean or Middle East Maritime Alps (April 1976) Maritime Alps (October 1976) Northeastern Brazil Northern Chile Tropical islands Meteoric line (%) dD 8d O 10 dD 8:1+1d18 O 11+1 dD 8d18 O 22


Reference Craig (1961a) Dansgaard (1964) Gat (1971) Bortolami et al. (1978) Bortolami et al. (1978) Salati et al. (1980) Fritz et al. (1979) Dansgaard (1964)

dD 8:0+0:1d18 O 12:1+1:3 dD 7:9+0:2d18 O 13:4+2:6 dD 6:4d18 O 5:5 dD 7:9d18 O 9:5 dD 4:6+0:4d18 O 0:1+1:6

was characterized by a different local meteoric line. What should be checked in order to decide between these two possible explanations? The age. Groundwater data plotted in Fig. 9.8 fall along the meteoric line but reveal a large spread of values. Separation into shallow and deep waters revealed the

Fig. 9.6 Isotopic composition of water sampled from wells in central Manitoba, Canada. The values fall close to the local meteoric line dD 8:1d18 O 11. The researchers (Fritz et al., 1974) concluded that evaporation during recharge and isotopic exchange with aquifer rocks are insignicant.


Chapter 9

Fig. 9.7 Isotopic composition of groundwaters of northern Chile. The values lie below the meteoric line of local precipitation, explained by the investigators (Fritz, et al., 1979) as reecting secondary fractionation by evaporation prior to inltration, or the presence of ancient waters that originated in a different climatic regime. The large variations in the groundwater compositions are useful in local groundwater tracing.

Fig. 9.8 Isotopic composition of groundwaters near Chatt-el-Honda, Algeria. The values scatter along the meteoric line but reveal an internal order: values of deep groundwaters are isotopically lighter (more negative) than shallow groundwaters. This was taken as an indication that the deep groundwaters were ancient and originated from rains of a different climatic regime. This is supported by the large number of ancient deep groundwater water samples, as borne out by low 14C concentrations (sections 11.4 and 11.8). (From Gonantini et al., 1974.)

Stable Hydrogen and Oxygen Isotopes


latter have distinctly lighter isotopic compositions. A possible origin of ancient recharge at a different climatic regime was suggested in this case too. The necessary check has been done: the deeper waters, of light isotopic composition, were indeed found to contain little or no measurable 14C, indicating high groundwater ages (section 11.4) and supporting the paleoclimate hypothesis.

9.5 Temperature Effect

Dansgaard (1964) analyzed a large body of isotopic data gathered by the International Atomic Energy Agency and showed that temperature is the major parameter that determines the isotopic values of precipitation (Fig. 9.9). In his extensive discussion, Dansgaard summed up the knowledge gained in laboratory experiments and eld observations. The composition of precipitation depends on the temperature at which the oceanic water is evaporated into the air and, even more important, the temperature of condensation at which clouds and rain or snow are formed. The net effect is expressed in the following empirical function (from Fig. 9.9): d18 O 0:7Ta 13%; or 0:7%= C and, in a similar way, dD 5:6Ta 1000%; or 5:6%= C A local study at Heidelberg, Germany, revealed the following empirical function (Schoch-Fischer et al., 1983): dD 3:1+0:2Ta 172+3%; or 2:8+0:2%= C (Ta is the local mean annual air temperature.) The meteoric line (Fig. 9.4) is thus the result of the combined dD and d18O dependencies on temperature. The temperature effect is well seen in seasonal variations in regions with rains during cold and warm seasons. An elegant example from Switzerland is given in Fig. 9.10: monthly measurements in three stations revealed that the annual temperature cycle is followed by corresponding changes of d18O. The temperature dependence of the isotopic composition of precipitation, or temperature effect, is to a large extent responsible for the large variation in the isotopic composition of groundwaters, thus equipping the hydrologist with a powerful tool. In regions with summer and winter precipitation the isotopic differences in the composition of the precipitation are traceable as winter recharge and summer recharge fronts, important in establishing groundwater velocities and identifying piston ows.


Chapter 9

Fig. 9.9 Temperature effect. Correlation between annual mean d18 O values observed in precipitation and the annual mean temperature of local air: polar ice (circles and triangles; gures in parenthesis indicate total thickness in cm); continental precipitation (.) and island precipitation (). (From Dansgaard, 1964.)

9.6 Amount Effect

Figures 9.119.13 show the dependence of the isotopic composition on the amount of rain: heavier rain events, or greater monthly precipitation amounts, result in more negative dD and d18O values. Dansgaard (1964) proposed two major explanations for this amount effect: . . Lower ambient temperatures cause the formation of clouds with lighter isotopic composition (temperature effect, Fig. 9.9); lower temperatures also cause heavier rains. Falling raindrops undergo evaporation, enriching the falling rain in the heavy isotopes. This effect is less severe both when ambient

Stable Hydrogen and Oxygen Isotopes


Fig. 9.10 Monthly mean d18 O values in precipitation and monthly mean air temperatures from 19711978 for Swiss stations. The value of January (1) is shown twice to complete the cycle. The d18 O values are seen to covary with the temperature, reecting a pronounced temperature effect of 0.350.5% d18 O= C. The measurements, carried out at three stations of different altitudes, revealed an altitude effect, precipitation at higher altitudes having isotopically lighter compositions. (From Siegenthaler and Oeschger, 1980.)

Fig. 9.11 Two cases of isotopic compositions varying with the amount of precipitation (the amount effect), reported by Dansgaard (1964). Left, Binza (Leopoldville), Congo; right, Wake Island. The d18 O precipitation values are for individual months. The amount effects were 2.2% d18 O=100 mm rain for Binza and 1.6% d18 O=100 mm rain for Wake Island.


Chapter 9

Fig. 9.12 Amount effect. Monthly rain and d18 O values measured for three years at Rowen Boos, Haute Normandie, France. Dots, October 1974December 1975; x, 1976 and 1977. Rainier months reveal isotopically lighter rain. (After Conrad et al., 1979.)

Fig. 9.13 Amount effect. Monthly rain and d18 O values of northeastern Brazil plotted as a function of sampling date. The curves are mirror images, revealing low d18 O values at the high rain months. (From Salati et al., 1980.)

Stable Hydrogen and Oxygen Isotopes


temperatures are low and when the amount of rain is large (as the air gets more saturated). The amount of monthly rain varies during the year, causing a seasonal variation in the isotopic composition. This point is demonstrated in a case study from northeastern Brazil (Fig. 9.13).

9.7 Continental Effect

Several workers noticed that the average isotopic composition of precipitation tends to have more negative values further away from the ocean coast. This continental effect is well reected in European groundwaters (Fig. 9.14). The explanation lies in the history of the precipitating air masses. As they travel inland, rain is gradually precipitated by condensation, accompanied by more efcient condensation of water molecules with heavier isotopes (opposite to evaporation). The residual moisture in the air masses thus becomes gradually lighter in its isotopic composition, and lighter rain is progressively formed. The continental effect is often masked by other effects, for example, temperature (seasonal) effect and, as discussed in the next section, altitude effect.

Fig. 9.14 Lines of equal dD values for Europe, based on over 300 samples of groundwater. A trend of lighter isotopic composition is seen as a function of the distance from the ocean, reecting the continental effect in the precipitation. (After Sonntag et al., 1979.)


Chapter 9

9.8 Altitude Effect

The altitude effect is seen in Fig. 9.15. The d18O values in Swiss precipitation are lighter with higher altitudes. The gradient, or altitude effect, is 0.26% d18O/100 m altitude. The altitude effect is observed in this case to be the same in the precipitation and in the derived surface and groundwaters. This effect is not masked by the seasonal temperature effect (Fig. 9.10). The altitude effect has to be established in each study area. Leontiadis et al. (1983) reported a value of 0.44%/100 m for the part of Greece that borders Bulgaria. As clouds rise up the mountains, the heavy isotopes are depleted and the residual precipitation gets isotopically lighter. This effect turns out to be an effective tool in tracing groundwater recharge. Payne and Yurtsever (1974) reported a case study in which isotope hydrology was recruited to nd out to what extent groundwaters in the Chinahdega Plain, Nicaragua (1100 km2, 200 masl), were recharged by local precipitation on the plain or by recharge from the higher slopes of the Cordillera Mountains (up to 1745 m). They worked in three stages: . They analyzed d18O in weighted mean precipitation samples from different altitudes and dened an altitude effect of 0.26%/100 m (Fig. 9.16).

Fig. 9.15 Variations of mean d18O as a function of altitude for Swiss precipitation (.), groundwaters (x), and rivers (~). The lines are parallel, all revealing an altitude effect of 0.26% d18O/100 m. (From Siegenthaler and Oeschger, 1980.)

Stable Hydrogen and Oxygen Isotopes


. .

They analyzed groundwaters with known recharge altitudes and found the same altitude effect (Fig. 9.17). They measured the d18O of the studied waters in the plain and established the ratios of local plain recharge (around 25%) to mountain recharge.

A nice control was tritium, found to be higher in wells with higher plain-recharge contributions, revealing shorter travel times, as compared to low tritium contents in wells with higher contributions of mountain recharge (longer travel times). The altitude effect is applied in an ever-growing number of studies as a tool to calculate the recharge altitude from the deuterium and d18O data of springs and wells. Hence, much interest lies in a study of Bortolami et al. (1978), who checked the accuracy of such calculations in a case study in the Italian Maritime Alps. They conducted the following measurements: dD and

Fig. 9.16 d18O values in mean weighted samples of precipitation from different altitudes in Nicaragua. The lines for 1969 (A) and for 1970 (B) are quite parallel, the average (line C) revealing an average altitude effect gradient of 0.26% d18O/100 m. (From Payne and Yurtsever, 1974.)


Chapter 9

Fig. 9.17 Altitude effect, reected in groundwater of known recharge areas, Nicaragua. An effect of 0.26% d18O/100 m is obtained, the same as observed for the regional precipitation (see Fig. 9.16). (From Payne and Yurtsever, 1974.)

d18O in precipitation in stations of various altitudes during one winter month (October 1974) and one summer month (April 1976). The data (Fig. 9.18) revealed different lines for the winter and summer d18O values, and only one line for dD. The corresponding altitude-isotope equations were found from Fig. 9.18 to be d18 O 3:126103 h 8:03 and dD 24:96103 h 51:1 where h is the altitude in meters above sea level (masl). Accordingly, two altitude equations can be written: h 320 d18 O 2564 and h 40:2 dD 2052

Stable Hydrogen and Oxygen Isotopes


Fig. 9.18 Isotopic compositions, as a function of altitude, for precipitation samples collected in a summer month (April 1976) and a winter month (October 1974), Maritime Alps. The data were used to establish local altitude effect equations (see text). Winter and summer d18O values fall on separate lines, reecting the difference in the origin of the precipitating air masses from the Atlantic and Mediterranean, respectively. (After Bortolami et al., 1978.)

In the second stage, samples were collected for isotopic analysis in the karstic Bossea Cave, at an altitude of 810 masl. The data, given in Table 9.2, were used individually to calculate recharge altitudes. The agreement between hD and h18O is good in the various samples, but the agreement between repeated samples is rather poor. Values of calculated recharge altitude vary from 11801871 m. This is a highly discouraging range of values, showing that calculations based on single water samples are


Chapter 9

Table 9.2 Recharge Altitude Calculated from dD and d18O in Repeatedly Collected Samples in the Bossea Cave, Maritime Alps, Italy (810 masl) Date 13-10-74 7-3-76 9-4-76 18-4-76 25-4-76 1-5-76 14-5-76 30-5-76 6-6-76 dD (%) 81.4 88.4 94.4 97.3 97.6 90.2 85.8 87.6 87.5 Average 89.93

d18O (%) 11.70 12.86 12.86 13.83 13.85 12.91 12.34 12.54 12.51 12.82

hD (m) 1220 1502 1743 1859 1871 1574 1397 1470 1465 1565a 1563b

h18O (m) 1180 1551 1551 1861 1868 1567 1385 1449 1440 1539a 1538b

Average of recharge altitudes calculated via dD and d18O. Calculation based on average dD 89.9% and average d18O 12.82%. Source: Data from Bortolami et al. (1978) applying their average equation for the local precipitation: h 320 d18O 2564 and h 40.2 dD 2052 (see text).

unreliable. The average hD and h18O values, 1565 m and 1539 m, seem however to be very reasonable as average recharge altitudes for the water sampled in the Bossea Cave. The calculations based on the average dD and d18O values are practically identical to the earlier ones: 1563 and 1538 m. The research of Bortolami and his coworkers (1978) provides an excellent example of a study aimed at a local calibration of an isotopic tracing technique. The variability observed between results of single samplings is probably extreme, since they worked on a karstic system which has a rapid response to individual storm events.

9.9 Tracing Groundwater with Deuterium and Local Studies


In a work on South African warm springs, the question arose whether their temperature and dissolved ions represent the water at depth, or did intermixing with shallow cold water take place, especially from adjacent rivers. Hence, dD and d18O were measured in the thermal springs and the nearest rivers (Mazor and Verhagen, 1983). The results are shown in Fig. 9.19. It is seen that the thermal springs have signicantly more negative values than the nearby rivers, indicating that no intermixing took place

Stable Hydrogen and Oxygen Isotopes


Fig. 9.19 Isotopic composition of thermal waters (s) and adjacent rivers (.) in South Africa. The lines connect thermal springs with the nearest river. It is seen that the spring waters are signicantly lighter than the nearby rivers, indicating that no (or negligible) intermixing occurred. (From Mazor and Verhagen, 1983.)

except in one case. This conclusion has been supported by the practical absence of measurable tritium in the thermal springs, indicating long travel times. What might be the reason for the lighter isotopic composition of the South African warm springs, as compared to the river waters, as seen in Fig. 9.19? Three explanations can be offered: . . . An altitude effect, caused by spring recharge in higher elevations. This would agree with the increased temperatures, indicating relatively deep circulation. The waters might be ancient, belonging to a different climatic regime (paleowaters). The river waters were heavy at the time of sampling, in the context of the seasonal variations.

The uncertainty regarding the causes of the isotopic differences did not intervene in the application of this difference to a tracing problem (nonintermixing of thermal and surface waters). Rivers and shallow groundwater are often saline in arid or semiarid regions. Examples are common in northeastern Brazil in crystalline rocks, remote from the sea, and in regions where no marine transgression has occurred for 100 million years. Hence, evaporation was for a long time


Chapter 9

suspected to be the cause of the rise in salinity. The problem was studied by examining Cl and d18O (Fig. 9.20). In general, the Cl and d18O curves covaried during the months of observation, proving that evaporation caused the salinity (Salati et al., 1980). A variance is seen in the details of the peaks of the two curves in Fig. 9.20, such as the peak dened by the last three points. This might be explained by special rain events, for example, a summer rain that underwent much evaporation during descent to the ground (resulting in more positive d18O), which lowered for a short while the chlorine concentration in the river water (at the low-ow season). In shallow groundwaters, at a depth of about 1 m, in the Chott-elHonda salt plain in inland Algeria, a positive correlation was observed between dry residue (salinity indicator) and d18O (Fig. 9.21). Evaporation through the thin soil cover was deduced (Gonantini et al., 1974). This conclusion has been conrmed by the more saline water lying on an evaporation line in a dDd18O diagram (Fig. 9.22). The stable isotopes of water are most useful in tracing seawater intrusions, so troublesome in coastal urban areas. One example is seen in Fig. 9.23 for wells west of Hermosillo, Gulf of California.

Fig. 9.20 Chloride and d18O values in repeatedly collected samples of the Pajeu River, northeastern Brazil. A general correlation is seen, revealing the role of evaporation, most important during July (rise in ambient temperatures and low river ow). (From Salati et al., 1980.)

Stable Hydrogen and Oxygen Isotopes


Fig. 9.21 Isotopic composition and salinity (dry residue) in shallow wells south of the Chott-el-Honda salt plain, Algeria. Evaporation is evident, but a further check can be seen in the next gure. (From Gonantini et al., 1974.)

Table 9.3 reports data on depth proles in coastal wells of the Salentine Peninsula, Italy. Which trends can be seen, and what is their meaning in terms of groundwater movement? In general, temperature, C1, dD, d18O, and d13C values are high in the deeper parts of the wells, reecting seawater encroachment. The temperature gradient is caused by the regional

Fig. 9.22 Isotopic composition of groundwaters south of Chott-el-Honda, Algeria. The shallow groundwaters lie on an evaporation line, and the degree of heavy isotope enrichment agrees with the salinity (the sample numbers are the same as in the previous gure). (From Gonantini et al., 1974.)


Chapter 9

Fig. 9.23 Chlorinity and isotopic composition for coastal wells, Hermosillo, Gulf of California. The percentage seawater inltration can be calculated for each well. A mixing line is seen, its curvature being caused by the use of a logarithmic chloride axis. (From Payne et al., 1980.)

geothermal gradient. Practical hydrological conclusions can be reached with regard to desired pumping management of these wells, that is, lling up lower parts of wells, and/or limited pumping rates of fresh water only.

9.10 Tracing Groundwater with Deuterium and Regional Study


O: A

Stahl et al. (1974) provided an excellent example of isotopic tracing of ground-water, in the Sperkhios Valley, Greece (insert in Fig. 9.24). The research followed the following logical steps: 1. Artesian wells were grouped according to their dD and d1 8O values and geographical distribution. Three such groups emerged (Table 9.4 and Fig. 9.25). 2. Springs for which the recharge altitude could be deduced from eld data were analyzed and an isotopealtitude graph was established, dening the local altitude effect (Fig. 9.26). 3. The recharge altitudes of the three artesian well groups were determined with the aid of the altitudeisotopic composition

Table 9.3 Water Depth Proles in Coastal Wells in the Salentine Peninsula, Italy Date 17.4 18.4 18.2 17.4 17.5 17.5 17.5 17.4 18.0 17.0 17.0 17.1 17.2 17.4 16.8 16.8 17.1 17.1 17.2 17.5 19.4 19.4 16.6 18.4 29.2 59.8 114.8 39.5 42.0 54.9 55.2 594.9 594.3 31.9 44.0 581.9 55.4 580.2 2.3 37.8 562.3 565.2 7.3 12.3 587.3 594.3 15.4 581.5 593.2 583.4 5.94 6.15 4.29 6.23 6.24 6.20 6.12 2.40 2.53 5.24 5.63 2.36 5.48 2.40 4.37 6.00 2.68 4.93 4.79 2.65 4.59 2.46 2.42 2.25 5.5 5.3 4.2 5.9 5.7 5.7 5.6 1.8 1.7 5.4 5.3 1.3 5.1 1.3 5.1 4.9 1.0 0.8 6.10 5.9 1.2 1.4 5.0 1.3 1.3 0.8 34.5 33.5 26.5 33.5 33.0 32.0 32.0 10.0 11.0 31.5 31.0 8.5 29.5 8.5 31.0 30.5 6.3 6.1 36.1 34.0 7.5 9.2 33.5 9.0 9.0 7.5 10.70 9.50 9.54 10.80 11.30 10.70 12.10 7.09 5.17 11.84 13.40 5.00 13.93 3.70 14.37 11.30 8.87 7.60 14.40 13.32 5.61 5.29 10.90 4.09 3.30 2.60 8C

Stable Hydrogen and Oxygen Isotopes

No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 28 29
Source: Data extracted from Cotecchia et al. (1974).

Source Boraco Spring 9-2-71 Chidro Spring 3-2-71 Iduse Spring 14-7-71 CH well, 40 m 2-2-71 69 m 2-2-71 86 m 3-2-71 118 m 2-2-71 147 m 30-7-71 170 m 30-7-71 S-1 well, 19 m 9-7-71 30 m 9-7-71 40 m 13-7-71 S3 well, 9 m 13-7-71 19 m 13-7-71 C-S well, 56 m 23-2-71 108 m 24-2-71 175 m 25-2-71 184 m 9-12-72 30 m 17-2-71 70 m 18-2-71 SR well, 146 m 19-2-71 154 m 5-12-72 C-S well, 33 m 14-7-71 70 m 14-7-71 Ionian Sea 13-7-71 Adriatic Sea 14-10-73

Cl (meq/l) HCO3 (meq/l) d18O(%) dD (%) d13C (%)

C (pmc) 41.1 24.3 52.7 35.1 49.8 35.7 30.4 5.5 64.0 65.4 46.7 66.9 92.6 77.2 1.4 64.2 55.8 1.8 51.4 31.7 111.9 81.0


204 Chapter 9 Fig. 9.24 General map of study area in the Sperkhios Valley, Greece. The recharge altitudes (H) were calculated from deuterium and 18O data. (From Stahl et al., 1974.)

Stable Hydrogen and Oxygen Isotopes


Fig. 9.25 Isotopic data of artesian wells and springs in the Sperkhios Valley. Three well groups, or isotopic provinces, were recognized. A local meteoric line, dD 7d18O 6, was established from the spring data. (From Stahl et al., 1974.)

Fig. 9.26 Isotopic composition and recharge altitude of springs in the Sperkhios Valley. (From Stahl et al., 1974.)


Chapter 9

graph (Fig. 9.26), calibrated by the springs of known intake altitudes. The values are given in Table 9.4. 4. Once the three well groups and their corresponding recharge altitudes were obtained, the details of local ow (Fig. 9.24) were worked out by additional chemical, radioisotope, and eld data. 5. A group of saline (2.514.5 g C1/1) and warm (28 8C40 8C) springs and wells in the eastern part of the study area were suspected by earlier workers to contain a seawater component. This was tested and conrmed by C1d18O relations, and the percentage of seawater intermixed in each case could be calculated (Fig. 9.27).

9.11 The Need for Multisampling

In the previous sections the many factors that determine the isotopic composition of groundwater have been described. Many of these, especially the temperature, vary seasonally, while others, such as the intensity of rain, vary from one rain event to another. As a result, single samples may be nonrepresentative. Table 9.5 gives examples for the variations between daily precipitation events for a single station. Signicant variations in the isotopic composition were seen in water samples collected in a pond (Fig. 9.1), rain samples collected at different dates (Fig. 9.5), water samples from adjacent wells (Fig. 9.6), samples from wells of different depths (Fig. 9.8 and Table 9.3), precipitation samples of various months (Fig. 9.10), rains of different intensities (Fig. 9.11), summer and winter precipitation (Fig. 9.18), or river samples collected during a whole season (Fig. 9.20). The basic conclusion from these variations is the necessity of multi-sampling. The hydrochemist has to plan the sample collection in the right way in order to get enough data for the calculation of meaningful average values and to gain an insight into the ne structure of the investigated system in the lateral, vertical, and time dimensions.

Table 9.4 Isotopically Deduced Average Recharge Altitudes for Artesian Well Groups in the Sperkhios Valley Well group I II III Average d18O (%) 9.36 + 0.04 8.81 + 0.07 7.80 + 0.15 Average recharge altitude (masl) 1350 950 250

Source: Following data by Stahl et al. (1974).

Stable Hydrogen and Oxygen Isotopes


Fig. 9.27 Isotopic composition and chlorinity of warm springs at the Bay of Maliakos (see Fig. 9.24). Values lie on a mixing line with seawater, proving that the last one is intermixing in the mineral springs. (From Stahl et al., 1974.)

Table 9.5 Variations in d18O Values in Daily Rain at Ashdod, Israel Date (Jan. 1968) 6 9 10 14 15 16 17 21 23 24 28 30 31 Amount (mm) 5.3 6.5 1.0 12.5 10.1 5.2 3.3 3.4 2.4 13.0 7.1 10.7 7.6 d18O (% SMOW) 5.01 + 0.06 2.09 + 0.06 0.14 + 0.07 6.13 + 0.07 6.43 + 0.13 2.05 + 0.13 2.3 + 0.11 4.70 + 0.11 2.70 + 0.10 5.27 + 0.11 3.09 + 0.11 4.15 + 0.11 6.90 + 0.11

Source: From Gat and Dansgaard (1972).


Chapter 9

Note: An excellent collection of basic isotope data and discussion of case studies is provided by publications of the International Atomic Energy Agency, included at the end of the reference list. Especially useful is the collection of papers in Stable Isotope Hydrology: Deuterium and Oxygen-18 in the Water Cycle, IAEA, Vienna, 1981. Fritz and Fontes (1980 and 1986) are the editors of the Handbook of Environmental Isotope Geochemistry, which contains valuable information on the stable hydrogen and oxygen isotopes.

9.12 Sample Collection for Stable Hydrogen and Oxygen Isotopes and Contact with Relevant Laboratories
In principle, sampling is easy. A 100-ml sample is adequate for stable isotope analyses. The main precaution to be taken is to keep the bottle well closed in order to avoid any evaporation. It is highly recommended that sample collection be discussed with the respective laboratory experts. The hydrochemist has to be familiar with analytical difculties, for example, the presence of H2S, traces may interfere with the mass spectrometric measurements. It is always recommended to take double samples and keep one as a backup sample. These can be used in case of doubt concerning the obtained results. Samples have to be collected properly. In a spring the sample should be collected as deep as possible from the surface of the water body of the spring eye, a topic also discussed in section 7.1.

9.13 Summary Exercises

Exercise 9.1: From the information included in Fig. 9.2, calculate the percentage of Dead Sea brine intermixed in the Hamei Yesha mineral spring. Do the calculation using the redundant information available, that is, use the dD and the d18 O values. Exercise 9.2: Check the hD and h18O calculations in Table 9.2. Applying the same altitudeisotopic composition equations, calculate the average recharge altitude for (a) a well with a mean annual value of dD 85:5% and (b) a spring with a steady discharge and a value of d1 8O 12:4%. Exercise 9.3: What other measurements could you recommend to further check the evaporation process concluded to operate in the Pajeu River (Fig. 9.20)?

Stable Hydrogen and Oxygen Isotopes


Exercise 9.4: Examine Fig. 9.8. The points with light isotopic composition are postulated to indicate water that was recharged under different climatic conditions. Which type of climate could it be? Exercise 9.5: Examine Fig. 9.18. It represents a study aimed to calibrate which parameter? How will you select sampling points for a similar calibration in your case study areas? Exercise 9.6: Examine Fig. 9.22. Which boundary conditions can be deduced for groundwater samples 5659? Exercise 9.7: The solubility of HCO3 decreases or increases as a function of salinity? Retrieve the answer from a close examination of the Salentine Peninsula data given in Table 9.3. From this set of data, is the HCO3 conrming the conclusion discussed in the text concerning the observed composition changes in the depth proles of the reported wells? Exercise 9.8: The seawater dilution (mixing) curve, seen in Fig. 9.23, is curved. How can the same data be plotted so they will fall on a straight mixing line?


10.1 The Radioactive Heavy Hydrogen Isotope

Tritium is the heavy isotope of hydrogen (section 5.2). Its symbol is 3H, or T. Tritium atoms are unstable and disintegrate radioactively, forming stable 3 He atoms. The radioactive decay is accompanied by the emission of b particles, measurable in specic laboratories: T b 3 He ?

The rate of radioactive decay is by convention expressed as the half-life, T1/2, dened as the time span during which a given concentration of the radioactive element atoms decays to half their initial value. T1/2 of tritium is 12.3 years. Thus, after 12.3 years one-half the initial concentration of tritium atoms is left, after 24.6 years only one-quarter is left, and so on. A radioactive decay curve of tritium is given in Fig. 10.1. Using the decay curve it is possible to determine, for example, how many years it takes for a given amount of tritium to decay to 20% of the initial amount. The answer, obtained from Fig. 10.1, is 29 years. Similarly, one can determine what percentage of an initial amount of tritium will be left after 20 years. The answer is 32% (read from Fig. 10.1). The concentration of tritium in water is expressed by the ratio of T atoms to H atoms: T=H 1018 is defined as 1 tritium unit1 TU

Tritium Dating


Fig. 10.1 Radioactive decay curve of tritium. After 12.3 years 50% of an initial concentration is left; after 24.6 years 25% is left, etc.

10.2 Natural Tritium Production

Cosmic ray neutrons interact in the upper atmosphere with nitrogen, producing 15N, which is radioactive and disintegrates into common carbon (12C) and tritium:





C 3H

The tritium atoms are oxidized to water and become mixed with precipitation and so enter the groundwater. The natural production of tritium introduces about 5 TU to precipitation and surface water. In the saturated zone, water is isolated from the atmosphere and the tritium concentration drops due to radioactive decay: the original tritium concentration of 5 TU drops to 2.5 TU after 12.3 years, only 1.2 TU are left after another 12.3 years, and so on. Provided the natural production of 5 TU is the only source of tritium in the groundwater, we would have at hand a water dating tool. For example, water pumped from a well with 3 TU has preserved 3 6 100/5 60% of its natural tritium content, equivalent to an age of 9 years (readable from Fig. 10.1). However, a hydrologists life is not that simple. Most aquifers have a capacity equal to several annual recharges, or, in other words, water accumulates in the aquifer for many years and the age we have just calculated from the tritium concentration is not a real age, but rather an


Chapter 10

average or effective age. This is still of high value in hydrology. Tritium measurements have a practical limit of 0.2 TU. Assuming an initial input of 5 TU, an amount of 0.2 TU represents 0.2 6 100/5 4%, or an age of 55 years (Fig. 10.1). Thus the tritium method of effective hydrological age seems valid in the range of a few decades. Low tritium concentrations are determined on samples that have been preconcentrated electrolytically, necessitating samples of about 300 ml. To allow for repeated measurements, samples of 11 should be collected for tritium measurements.

10.3 Manmade Tritium Inputs

Nuclear bomb tests, which began in 1952 in the northern hemisphere, added large amounts of tritium to the atmosphere. They reached a peak in 1963, with up to 10,000 TU in a single monthly rain in the United States. An international treaty stopped surface nuclear bomb tests in 1963, and tritium concentrations in precipitation decreased steadily. Since nuclear testing began, tritium (and dD and d18O) has been measured in a worldwide net of stations (Fig. 10.2), coordinated by the International Atomic Energy Agency (IAEA) in Vienna. The results are published in annual reports: Environmental Isotope Data: World Survey of Isotope Concentration in Precipitation, IAEA, Vienna. Figure 10.3 represents annual tritium concentrations in precipitation at various stations from 19611975. Figure 10.4 reveals monthly values for several stations for the period 19611965, when the bomb-tritium impact was especially high. The following patterns are seen in the tritium curves: . . . Values rose much higher in the northern hemisphere, where the bomb testing took place. The maximum peak was reached in 1963, and values decreased thereafter. A summer peak and winter low were seen each year (Figs. 10.4 and 10.5), reecting the fact that the tritium was displaced in large amounts in the higher parts of the atmosphere and leaked in the spring and summer into the lower parts.

The manmade tritium, which reached several thousand TU in precipitation during 1963, completely masked the natural tritium production discussed in the previous section. The awareness of the potential importance of tritium to hydrology arose only after the nuclear tests began. By that time the natural tritium content in precipitation could no longer be measured, but a unique solution was foundmeasurements in stored and dated wine bottles,

Tritium Dating Fig. 10.2 Network of weather stations collecting precipitation samples for tritium and stable hydrogen and oxygen measurements, coordinated by the International Atomic Energy Agency, Vienna. 213


Chapter 10

Fig. 10.3 Annual weighted average tritium concentrations of representative weather stations. Values increased dramatically in 1963 and have been steadily decreasing ever since. Values are much higher in the northern hemisphere (where the nuclear tests took place). At present the tritium concentrations are almost back to natural values. [From Environmental Isotope Data: World Survey of Isotope Concentrations in Precipitation, vol. 1 (1969) and vol. 7 (1983).]

reecting the relevant annual rains (Table 10.1). A common value for prebomb tritium is 5 TU. The described observations may be applied to practical problems. For example, the weighted average tritium concentration in Vienna was 3280 TU in 1963 (Fig. 10.3). How much tritium would be left in water that was recharged in 1963 and pumped in a well in 1988? The answer can be found by using the following steps: 1988 1963 25 years passed. From Fig. 10.1 one can read that after 25 years only 25% of the initial tritium is left. 3280 6 25/100 820 TU would be left in 1988. Before 1952, natural tritium was about 5 TU in precipitation. How much would be left in groundwater recharged in 1951 and emerging in a spring in 1988? The answer can be found by using the following steps:

Tritium Dating


Fig. 10.4 Monthly tritium concentrations in rain at representative stations. Summer peaks indicated that bomb tritium was stored in the high parts of the atmosphere and leaked in the spring into the lower atmosphere. (From IAEA Technical Report No. 73, 1967.)


Chapter 10

Fig. 10.5 Summer peaks and winter lows of tritium observed in precipitation in Sweden. (From Pearson, 1974.)

37 years passed. Radioactive decay would have decreased the concentration to 11% of the initial value (Fig. 10.1). 5 6 11/100 0.5 TU would be left in 1988.

10.4 Tritium as a Short-Term Age Indicator

When the anthropogenic tritium was noticed, hopes arose that the specic tritium pulses, contributed by the individual tests, would provide a way to accurately date groundwater. However, it turned out that the input values in precipitation varied considerably from one location to another and from one season and year to the next. In addition, complicated mixing takes place in each aquifer, and the mode and extent of mixing of each years recharge

Table 10.1 Estimates of Natural, Pre-Bomb, Tritium Concentrations in Precipitation and Wine (following Vogel et al. 1974) Locality Rhone valley, France Bordeaux, France Rhine valley, Germany New York State, USA Chicago, USA Ottawa, Canada Greenland Sample Wine Wine Wine Wine Wine Rain Ice TU 3.4 4.3 5.5 5.8 7.5 15.3 12.6

Tritium Dating


with that of previous years recharge is unknown. Hence, age determinations accurate to the year are impossible and of no meaning to groundwater studies. However, semiquantitative dating is possible and very informative: . . . Water with zero tritium (in practice < 0.5 TU) has a pre-1952 age. Water with signicant tritium concentrations (in practice > 10 TU ) is of a post-1952 age. Water with little, but measurable, tritium (0.510 TU ) seems to be a mixture of pre-1952 and post-1952 water. The topic of water mixtures is further discussed in section 11.10, along with 14C data.

10.5 Tritium as a Tracer of Recharge and Piston Flow: Observations in Wells 10.5.1 Tritium Concentrations and Time Series Providing Insight Into the Local Recharge Regime
Seasonal variations in the tritium concentration in two shallow tribal wells in the Kalahari are seen in Fig. 10.6. Variations in tritium were noticed to follow variations in the water table. This observation provided insight into the local recharge mechanism. The tritium-rich recharge of the rainy season formed an upper layer in the aquifer. As abstraction, mainly during the dry season, advanced lower water layers were encountered, having been stored in the aquifer for several years. The seasonal tritium peak was observed to arrive at the wells several months after the rain peak. Thus the recharge water moved in the aerated zone not through conduits, but in a porous

Fig. 10.6 Seasonal variations in tritium concentration in shallow wells in the Kalahari, indicating recharge in a piston-ow mode. (From Mazor et al., 1973.)


Chapter 10

medium, in a piston ow mode (section 2.1, Fig. 2.2). The time lag provided an idea of the storage capacity of the aerated zone.

10.5.2 Tritium in Soil Proles Applied to Assess Inltration Velocity

Several workers measured tritium concentrations in proles of soil moisture. The samples were collected in most cases by means of a hand drill; the prole samples were carefully wrapped to avoid drying or exchange with tritium in the air. In the laboratory the soil moisture was extracted by distillation, weighted (to get a moisture prole), and measured for the tritium concentration. Figure 10.7 deals with such a prole from South Africa, along with the local precipitationtritium curve. The prole was taken in December 1971 and the precipitationtritium curve has been corrected (solid line, top of Fig. 10.7) for radioactive decay until that date. This corrected line indicates 7 TU for 1958 precipitation, an increase to over 20 TU in the rainy season of 1962, and over 30 TU for 1964. These values were applied to identify the time points marked on the tritiumdepth line in Fig. 10.7. The moisture with the 1958 tritium concentration was observed in 1971 at a depth of about 2 m. The inltrating water moved 2 m in 13 years (1958 to 1971), indicating an average inltration velocity of 0.15 m/year. The 1962 tritium concentration was observed at a depth of 1.4 m after 1971 1962 9 years (1962 to 1971), indicating inltration velocity of 0.16 m/year; the 1964 tritium front was observed at 0.8 m, indicating an inltration velocity of 0.11 m/year. Variations in the calculated inltration velocity may occur due to differences in the soil properties or due to variations in the annual rain regimes. One may therefore retrieve from soil proles average recharge velocities, relative lateral and vertical conductivity (by comparing different proles), and recharge efciencies.

10.5.3 Tritium Proles Applied to Estimate Recharge Amounts

The applicability of the tritium prole data can be demonstrated by means of an example: a tritium front in a soil prole was identied as having descended 3 m during 10 years, and the weighted average moisture content was found to be 12% (by volume). These data can be used to calculate the average annual recharge: out of the 3-m prole, 3 6 0.12 0.36 m is the equivalent column of recharged water. The average annual recharge was 0.36/10 0.036 m, or 36 mm/year. Continuing with this example, if the

Tritium Dating


Fig. 10.7 Tritium in a soil prole from the Transvaal, South Africa, and in precipitation at Pretoria. The identication of the 1958, 1962, and 1964 moisture fronts is discussed in the text, along with the applications to calculate recharge percentage. (Following Bredenkamp et al., 1974.)

average annual precipitation was 650 mm/year, then the average recharge percentage was 36 6 100/650 5.5%. A second example: a tritium concentration signifying the 1962 peak was observed at a depth of 4.8 m in a soil prole with a weighted average moisture content of 12% by volume. The observation was made in 1978. The local average precipitation was 720 mm/year. What was the average inltration velocity and percentage? The average inltration velocity was 4.8/16 0.3 m/year; the equivalent recharge annual water column was 0.3 6 0.12 0.036 m, or 36 mm; and the recharge percentage was 36 6 100/ 720 5%.


Chapter 10

10.5.4 Active Rain Recharge in a Desert Indicated in a Tritium Soil Prole

Figure 10.8 shows tritium proles in soil moisture near Grootfontein, South Africa (Bredenkamp et al., 1974). A layered structure is seen, indicating a piston ow type of recharge in the soil. Another set of tritium soil proles from the southern Kalahari, South Africa, is given in Fig. 10.9 (Verhagen et al., 1979). The value of 10 TU was adopted to indicate the arrival of the 1963 tritium front. The results of this study are of special interest in the light of a

Fig. 10.8 Variations of tritium concentration with depth in soil proles near Grootfontein, South Africa. Such tritium proles were an excellent means of demonstrating piston ow of inltrating recharge water. (From Bredenkamp et al., 1974.)

Tritium Dating


long-standing controversy about whether recharge is effective at all in the sand-covered Kalahari dry land (Mazor, 1982). The 1963 recharge has penetrated 723 m, thus demonstrating active recharge. Prole B.H. 3 was taken below a large thorn tree. The depth of recharge penetration was only 8 m, about half the depth in the adjacent proles. This was attributed to the water consumption of the tree.

10.5.5 A Methodological Note: Soil Proles Overlook Water Flow in Conduits

Tritium proles are commonly interpreted with the basic premise that the soil is a uniform medium, with a spongelike structure, through which water inltrates. However, short-circuit ow through conduits such as cracks, bioturbations, or decayed root channels must also be considered. Cracks, or rodent holes, are efcient intake points of runoff, and occasionally they become lled with coarse particles, providing routes of relatively high conductivity. When a soil prole builds up, these coarsely repacked channels

Fig. 10.9 Tritium in soil moisture proles in the southern Kalahari, South Africa. The measurements were done in 1978, and 10 TU was taken to mark the 1963 recharge. B.H. 3 was proled under a large camel thorn tree. (From Verhagen et al., 1979.)


Chapter 10

of higher conductivity add up, forming a network of higher-conductivity conduits. The soil cores do not sample water owing in cracks or burrowed holes. Thus the inltration velocities and percentages, calculated by the above-discussed tritium soil proles, should be regarded as minimum values.

10.5.6 Tritium Applied to Identify Flow in Conduits

The importance of short-circuit inltration may vary signicantly from one area to another and its intensity may be measured by tritium measurements, e.g., in dripping water in shallow mines or in groundwater in at terrains: if, in such studies, tritium values encountered are higher than in the overlying soil proles, then short-circuit recharge has occurred. Such studies are meaningful in cases where lateral recharge can be excluded on grounds of local geology or topography (e.g., at terrain or hilltops).

10.5.7 Two Case Studies

Figure 10.10 provides data on repeated tritium measurements in a well and in the adjacent Mohawk River. What hydrological conclusions can be drawn? The variations in tritium concentrations in the well followed variations in the river, as shown in Fig. 10.10. Hence, the river is recharging the well. The time lag in the wells response can be used to calculate recharge velocities. The data reveal piston ow of the recharge water, with little smoothing by dispersion (Fig. 10.10). Tritium can also be used for regional recharge studies. An example from the Qatar Peninsula has been reported by Yurtsever and Payne (1979). They measured tritium in a large number of wells in a shallow aquifer, producing a map with isotritium contours (Fig. 10.11). Recharge occurred in areas of high tritium owing to areas of low tritium. The reader is referred to an article by Allison and Hughes (1975) discussing the use of tritium measurements to estimate the amount of recharge.

10.6 The Special Role of Tritium in Tracing Intermixing of Old and Recent Waters and Calculation of the Extrapolated Properties of the End Members
In sections 6.4 and 6.6 mixing of two water sources was discussed in terms of composition diagrams (Figs. 6.4, 6.11, and 6.176.19). The parameters of mixed waters plot on straight lines, but in most cases these lines are of positive correlations, for example, in the mixing of a deep warm water with a shallow cold water. In most cases the deep water also has a higher

Tritium Dating


Fig. 10.10 Repeated tritium measurements in a well and in the adjacent Mohawk River, New York, USA. The river was monitored for tritium by beta decay counting, and the results are expressed in pc/1 (1012 curie/l). (From Winslow et al., 1965.)

concentration of dissolved ions, and thus the deep water has higher values in all parameters. However, to obtain a negative correlation, we need a parameter that is high in one water and low, or zero, in the other water. Tritium is often such a parameter. In the example given in Fig. 10.12, the data indicate mixing of two water types. An upper limit of 39 8C is obtained by extrapolating the best-t line to zero tritium. Tritium serves as a sensitive check for possible intermixing of deep water with shallow water. For example, in a study of warm springs in Zimbabwe it was important to establish whether the sampled waters were indigenous to the deeper reservoirs or were intermixed with shallow water of the adjacent rivers (in several cases the spring emerges a few meters from the riverbed or in it). The tritium level in six warm springs (54100 8C) was 0.1 0.6 TU, as compared to 638 TU in nine river samples (Mazor and Verhagen, 1976). By comparing respective spring and river values it could be concluded that contamination by river water was less than 2%. The springs could be regarded, in this case, as single-component systems.


Chapter 10

Fig. 10.11 Isotritium lines (in TU) for wells in a shallow aquifer on the Qatar Peninsula. Recharge was from areas of high tritium (stippled on the map) to areas of low tritium. (From Yurtsever and Payne, 1979.)

Tritium Dating


Fig. 10.12 Tritium values from various springs and wells (letters) sampled on the same day in the spa of Vals, Switzerland. An extrapolation of the best-t line to zero tritium indicates an uppermost value of 39 8C for the warm end member (see text). (From Vuataz, 1982).

10.7 Tritium, Dissolved Ions, and Stable Isotopes as Tracers for Rapid Discharge Along Fractures: The Mont Blanc Tunnel Case Study
A unique study of the rockwater interrelation has been reported from the Mont Blanc tunnel by Fontes et al. (1979). The 11.6-km-long tunnel begins in a carbonate rock section in the Italian end, continues through a long section of granitic rocks, and ends in schist at the French end. The geological cross-section and chemical data are given in Fig. 10.13 and Table 10.2. A close correlation is seen in Fig. 10.13 between the lithological and chemical transects: . . . High HCO3 and pH and low Cl below the carbonate rock section, along with high Ca and Mg (samples I-36 and I-41 in Table 10.2). Low salt content in the granitic section (Fig. 10.13 and Table 10.2). Low HCO3 but relatively high and varying Cl in the schist section.

The last observation has been interpreted by the researchers as indicating the existence of evaporitic rocks in the schist complex, a conclusion that is supported by high Ca, Na, and SO4 concentrations in the water (e.g., sample F-1 in Table 10.2).


Chapter 10

Fig. 10.13 A geological cross-section and composition of waters sampled along the Mont Blanc tunnel. More data are given in Table 10.2 and in Fig. 10.14. The good correlation with the lithology is discussed in the text. (After Fontes et al., 1979.)

The chemistry of water encountered in the Mont Blanc tunnel is thus directly related to the lithological section. This was interpreted as indicating recharge along almost vertical joints, with little horizontal ow.

Tritium Dating


Table 10.2 Composition (ppm) of Representative Water Samples from the Mont Blanc Tunnel
Sample F-1 F-27 F-30 F-38 I-21 I-36 I-41 Lithology Schist Granite Granite Granite Granite Carbonates Carbonates pH 6.9 6.5 6.5 6.5 6.7 7.5 7.2 Ca2 27.6 23.1 9.22 9.20 9.20 26.8 32.8 Mg2 0.73 0.24 0.49 0.24 0.49 2.41 2.19 Na 18.4 10.7 13.3 21.3 5.04 8.70 9.39 K 2.97 1.17 1.17 2.35 2.74 0.78 2.35 Cl 8.90 3.54 4.62 5.33 3.55 5.32 3.55 SO4272.4 46.0 26.9 36.8 14.1 36.5 31.7 HCO3 22.0 29.3 25.6 28.7 30.5 67.1 75.6 SiO2 n.d. 20.9 14.5 15.7 5.6 6.9 n.d.

Source: From Fontes et al. (1979).

The tritium and stable isotopes results are given in Fig. 10.14, along with the surface prole and geological section. The tritium data indicate rapid recharge; all tritium values being post-bomb. By comparison with the Vienna line in Fig. 10.3, the values over 200 TU may be identied as post1961 recharge. The recharge area in the central section is at an altitude of about 3200 m (top of Fig. 10.14), and the tunnel is at an altitude of about 1300 m. Thus the recharged water descended 3200 1300 1900 m in 13 years or less, giving a recharge velocity of 150 m/year or more. The sharp variations in the tritium values indicate recharge ow in separated fractures, with varying ow velocities (reected by different tritium concentrations, indicating different intake dates). Comparison of the tritium data with the other parameters measured in the Mont Blanc tunnel is most instructive. The deuterium and 18O lines follow the topography (note that the dD and d18O scales were reversed in Fig. 10.14 to facilitate comparison with the topographic prole). The isotopic values are less negative at each end of the tunnel, reecting recharge from the lower parts of the respective landscape. The central part of the tunnel hosts water with more negative isotopic values, reecting recharge from higher altitudes. The average recharge altitude of the ends of the Mont Blanc tunnel and of the central part can be calculated using the isotopic altitude equations for the Maritime Alps (section 9.8): h 320 d18 O 2564 h 40:2 dD 2052 The dD curve in Fig. 10.14 reveals average values of 110% for the edges of the tunnel and 130% for the central part. The respective values of


Chapter 10

d18O are 15.2% and 17.5%. Applying these values to the altitude equations we get (in masl):

hD Tunnel ends Central section 2300 3170

h18O 2370 3040

Mean h 2330 3100

Fig. 10.14 Tritium, dD, and d18O in waters collected along the Mont Blanc tunnel during its construction in 1974. The dD and d18O axes have been plotted in a reverse mode to facilitate comparison with the topographic prole. The high tritium values indicate post-bomb recharge, and in the cases of over 200 TU one may even conclude post-1961 recharge (Fig. 10.3). (From Fontes et al., 1979.)

Tritium Dating


These results are in good agreement with the average altitude of the slopes of the ends and the average altitude of the central part of the topographic prole above the tunnel (even better agreement could probably be obtained if local isotopic altitude equations were available). The stable isotopes thus indicate independently that recharged water descends in vertical fractures. The combined application of dissolved ions, deuterium, and 18O supplied redundancy in the indications of ow in separated vertical channels, and the tritium provided the time scale or velocities. The above study is an example of the modes by which recharge through fractures can be identied, apart from sponge-type recharge. Dripping water in caves and mines is a good potential target for local studies of this type.

10.8 The Tritium-3He Groundwater Dating Method

The preceding sections dealt with a variety of hydrological applications of the manmade tritium signal. However, the tritium dating method has a number of shortcomings: . The method is based on the measurement of the concentration of tritium left in the sample, but the initial tritium concentration is taken from the records of tritium concentration in the local atmosphere; this concentration changes dramatically from one year to the next (Figs. 10.310.5 and 10.7). The uncertainty of the initial tritium concentration pertaining to a studied groundwater sample is so great that the method is only semiquantitative. Mixing patterns of newly recharged water and older groundwater are complex and poorly known, making the assignment of a particular initial tritium concentration to a studied case difcult. The tritium concentration in the atmosphere and in precipitation is almost back to the low natural concentrations, and the tritium concentrations in groundwater have also decreased signicantly. This is good news from an environmental point of view, but not for water researchers.

. .

During the last decade a different track has been followed for the tritium dating method, namely, measurement of the decay product 3He (section 10.1) as a substitute for the initial tritium concentration. Tritiumderived 3He (tritiogenic helium) is built up in the groundwater as the contained tritium disintegrates; hence, the 3H:3He ratio decreases with age. To facilitate the calculations both nuclides are expressed in TR (tritium ratio) units, that is, 3H: H and 3He:H ratios of 1018. In principle, the age of groundwater can be determined by measuring the tritium concentration left


Chapter 10

in the sample, the concentration of 3He accumulated in the sample, and knowledge of the half-life of the tritium disintegration, 12.3 years (Schlosser et al., 1988). This dating method is based on a number of assumptions: . . . The 3He can be identied based on the background of the atmospheric helium contained in every meteoric groundwater (Chapter 13). The 3He is retained in the sample or the diffusive loss is known. No 3He was gainedfor example, by diffusion from other groundwater bodiesor such gains can be estimated.

A major task in the tritium-3He dating method is the identication of He based on the background of the atmospheric helium, which has a 3 He:4He ratio that varies from one place to another within a wide range of values. The tritium-3He groundwater dating method is still in the investigation stage, but the number of researchers that apply it is growing, and commercial laboratories will probably soon accept samples for routine measurements. It seems that this method will extend the tracing of the 1960s tritium signal, so it can be used by the next generation of hydrologists. Even when the tritium in groundwater is no longer measurable, the presence of 3 He will indicate post-1952 recharge.

10.9 Sample Collection for Tritium Measurements

Sample collection for tritium concentration testing is simplesamples of 1 1 are adequate, exchange with the atmosphere has to be avoided by proper sealing, and it is preferred that samples be collected in glass bottles.

10.10 Summary Exercises

Exercise 10.1: In a well near Vienna, 30 TU were observed in 1965. What was the effective age of the water? Exercise 10.2: Archive data reveal that a well in the United States contained 1 TU in 1975. What was the effective age of the water? Exercise 10.3: An investigation was ordered to nd out whether a certain well was polluted by an adjacent sewage pond. The well contained 0.3 TU in 1973. What is your expert opinion? Exercise 10.4: What is the basic difference between the dating method based on the measured tritium peak and the developing tritium-3He method?


11.1 The Isotopes of Carbon

Carbon has three isotopes in nature: 12Ccommon and stable; 13Crare and stable; and 14Cvery rare and radioactive. The heavy carbon isotope, 14 C, is unstable and decays radioactively into 14N, emitting a beta (b) particle that can be measured in specialized laboratories. The half-life of 14C is 5730 years. The above information can be summarized in the following way:

b C ?14 N
T1=2 5730 years

The radioactive decay curve of 14C is given in Fig. 11.1. What fraction of an initial concentration of 14C is left after 10,000 years? The answer, read from Fig. 11.1, is 27%.

11.2 Natural


C Production

Carbon-14 is formed in the upper parts of the atmosphere from secondary neutrons formed by cosmic ray interactions with the atmosphere. The neutrons interact with common nitrogen:

N n ! 14 C 1 H

The 14C atoms are oxidized upon production and mixed with atmospheric CO2. With the latter the 14C is introduced into plants and into surface and


Chapter 11

Fig. 11.1


C decay curve (half-life 5730 years).

groundwater. Most of the 14C introduction into groundwater occurs through the soil CO2 (section 2.1), which in turn is in constant exchange with the atmospheric CO2 and, therefore, has similar concentrations of 14C. The concentration of 14C is expressed in relation to the 14C:12C ratio in an international standard (oxalic acid). The 14C concentration in the bulk carbon of the standard is dened as 100% modern carbon (pmc). Thus a tree that died will contain only 50 pmc after 5730 years (one half-life). The 14C concentration of a sample is measured in specialized counting laboratories. What is the 14C concentration of a tree trunk that fell 2000 years ago? The answer, read from Fig. 11.1, is 80 pmc. The analytical limit (including sample contamination) of the 14C measurement is in many cases about 1 pmc. What is the time range of the 14C dating method? The answer, again read from Fig. 11.1, is up to about 40,000 years. This limit may be extended by more sensitive measuring and sampling techniques. The 14C dating method has been carefully studied for archeological and paleoclimatic studies. Much effort has been invested in studying variations in the 14C production over the last 100,000 years. Minor variations have been observed, but they are negligible in ground-water dating, compared to other complicating factors.

Radiocarbon Dating


11.3 Manmade

C Dilution and Addition

Since the industrial revolution of the early nineteenth century, large amounts of fossil fuels (oil, coal, gas) have been combusted, causing an increase of about 10% in the concentration of atmospheric CO2. This added fossil CO2 was devoid of 14C and, correspondingly, lowered the 14C:12C ratio in the air by about 10%. An anthropogenic addition of 14C into the atmosphere occurred with the nuclear bomb testing from 1952 to 1963, along with the introduction of bomb tritium. As a result, the 14C concentration also increased in plants (Fig. 11.2), in the soil CO2, and in recharged groundwater. Values up to 200 pmc have been measured, but they decreased to about 120 pmc by 1987, and to about 110 pmc by 1995.



C in Groundwater: An Introduction to Groundwater Dating

Rain and surface water dissolve small amounts of atmospheric CO2. Signicantly more CO2 is added to water percolating through the soil layer, as soil air contains about 100 times more CO2 as compared to free air. Soil CO2 is produced by biological action such as root respiration and decay of plant material. This CO2 was tagged by the atmospheric 14C concentrations, that is, about 100 pmc in prenuclear bomb times (pre-1952) and up to 200 pmc in post-bomb years. Once water reaches the saturated zone of an aquifer it is sealed from the atmosphere and its 14C decays. Table 11.1 includes 14C and tritium data

Fig. 11.2 14C in plants in Germany and in Venezuela. Nuclear tests additions, above the natural 100 pmc, reached a peak value in 1964. (From Tamers and Scharpenseel, 1970.)


Chapter 11

Table 11.1 Carbon-14 and Tritium in Phreatic Groundwater in the Northern Kalahari No. 2 14 54 60 55 63 62 1 64 8 17 11 13 58 56 59 57 Well Makgaba 2 Rakops Khodabis 1231 Toteng 1242 Z1183 Gweta Bushman Pits Makgaba 1 Zoroya 1606 Steinbergs BH Tshepe Makoba Mahata Tsau Kuke Toteng 1320 Sehitwa tribal borehole

C (pmc)

Tritium (TU) 4.3 + 0.3 24.4 + 1.7 5.1 + 0.6 16.9 + 1.7 15.8 + 1.3 1.2 + 0.3 8.0 + 1.0 5.0 + 0.5 10.3 + 1.1 2.8 + 0.4 1.6 + 1.6 0.7 + 0.3 0.9 + 0.2 0.6 + 0.6 1.2 + 0.3

120.2 + 2.6 106.1 + 4.5 99.1 + 2.2 98.7 + 1.8 97.7 + 2.1 97.6 + 1.5 97.4 + 2.2 93.7 + 1.7 91.9 + 2.2 86.2 + 1.6 78.4 + 1.3 69.1 + 1.3 69.1 + 1.3 68.3 + 1.3 66.8 + 1.7 59.5 + 1.0 54.3 + 1.2

Source: From Verhagen et al. (1974).

from wells in the Kalahari desert. In two cases values above 100 pmc were seen, together with post-bomb tritium (samples 2 and 14). However, in other cases with post-bomb tritium, the corresponding 14C values were found to be below 100 pmc (Fig. 11.3). This lowering is not the result of radioactive decay, since the 14C half-life is too long for the decay to be noticeable in post-bomb samples. This lowering of 14C was caused by interaction with carbonate rocks devoid of 14C, a topic addressed in the next section. Results of a hydrochemical study in basaltic aquifers of Hawaii (Hufen et al., 1974) are given in Table 11.2 and in a histogram in Fig. 11.4. This case study is of special importance because it deals with basaltic aquifers, in contrast to carbonate aquifers, to be discussed in the following section. The tritium values in the Hawaii study were 0.32.9 TU in 1974, indicating that most or all of the water had a pre-1952 age. The corresponding 14C concentrations were 8597 pmc. The pre-1952 14C in the atmosphere was about 100 pmc. Hence, part of the waters reported in Table 11.2 maintained all their initial 14C, whereas others lost up to 15% of their initial value. This loss could occur for two reasons: (1) interaction with 14C-devoid carbonate rocks (secondary in the basaltic terrain) and (2) aging of the water, reected

Radiocarbon Dating


Fig. 11.3 Radiocarbontritium correlation, northern Kalahari groundwater (Table 11.1). Samples with values exceeding 85 pmc and 2 TU contain a post nuclear bomb water component. Dashed lines are theoretical dividers between prebomb and post-bomb waters. (From Verhagen et al., 1974.)

in radioactive decay of the 14C. We will return to the Hawaii study, discussing additional information provided by the 13C values. A case study of groundwater in the Chad basin, conducted during 1967 and 1968 (Vogel, 1970), revealed a wide spectrum of 14C concentrations from 0150 pmc (Fig. 11.5). Waters with over 100 pmc were clearly post-1952, demonstrating the possible use of 14C as an independent short-

Table 11.2 Carbon Isotopes and Tritium in Recent Groundwater in Basaltic Aquifers in Hawaii Draft CI HCO3 6 3 Pumping station (10 m /a) (mg/l) (mg/l) Aina Koa wells Waialae shaft Kaimuki wells Wilder wells Beretania wells Kalihi shaft Halawa shaft 0.57 0.47 7.43 10.79 12.76 15.89 17.20 134 135 76 43 52 73 46 82 102 76 107 73 69 67
13 Tritium Radiocarbon C (TU) (pmc) (d% PDB)

1.0 0.8 0.6 2.9 0.3 0.6 1.6

96.1 97.5 96.1 85.0 91.4 91.5 97.3

19.2 17.2 18.5 15.5 19.5 18.3 19.2

Source: From Hufen et al. (1974).


Chapter 11

Fig. 11.4 Histogram of radiocarbon and tritium in groundwaters in basaltic aquifers, Oahu Island, Hawaii. Pre-bomb (pre-1952) samples maintained nearly 100 pmc, indicating limited dilution by 14C-devoid carbonates (see text). (From Hufen et al., 1974.)

term age indicator, complementing the tritium method. The high 14C values further indicated that little dilution by 14C-devoid rocks occurred in water rock interactions. Waters with very low 14C also prevailed in the Chad study area, indicating the presence of old groundwater, tens of thousands of years old (several 14C half-lives).

Fig. 11.5 14C values in groundwater samples, collected during 1967 and 1968 in the Chad basin, Africa. Postnuclear bomb recharge is observed in several cases (greater than 100 pmc). Very old waters with low 14C were also common. (From Vogel, 1970.)

Radiocarbon Dating


11.5 Lowering of Rocks

C Content by Reactions with

Assume that water entered the saturated zone 4000 years ago with an initial concentration of 100 pmc and emerges at present in a well. How much 14C will it contain? The answer, read from Fig. 11.1, is 62 pmc. What should be the 14C concentration in a spring near Bonn, Germany, if the water was recharged in 1964 and emerged in 1982? From Fig. 11.2 it is seen that due to nuclear testing the atmospheric 14C concentration rose to about 180 pmc in 1964. This concentration would not be affected by radioactive decay in the 18 years that passed between recharge and emergence (the half-life being 5730 years). The last two hypothetical examples are correct only if the groundwater behaves as a closed system with regard to its 14C:12C ratio. Table 11.2 presents 14C data of basalt aquifers in Hawaii of mainly pre-bomb age, as reected in the low tritium concentrations. The waters are seen to contain up to 100 mg HCO3/l and have 14C values exceeding 91 pmc in seven out of eight reported pre-bomb cases. It seems, thus, that little or no 14C was lost due to reaction with rocks, and little or no dead carbon (i.e., devoid of 14 C) was added by interactions with aquifer rocks, a fact reected also in the low HCO3 concentration. In contrast, in the case of the Kalahari waters, reported in Table 11.1, notice the signicant lowering of the 14C content in recent, tritiumcontaining waters. This is a common observation, mainly in carbonate terrains. Limestone and dolomite contain no 14C because they were formed much longer ago than the 14C half-life of 5730 years. Recharged water containing CO2 reacts with the carbonates to form dissolved bicarbonate: H2 O CO2 CaCO3 ?Ca2 2HCO 3 100 pmc 0 pmc 50 pmc Thus the dissolved CO2 with 100 pmc reacts with the rock with 0 pmc to produce a 50 pmc bicarbonate. Similar reactions occur with silicates: H2 O 2CO2 2NaAlSi3 O8 ?2Na Al2 O3 6SiO2 2HCO 3 100 pmc 100 pmc or H2 O 2CO2 2KAlSi3 O8 ?2K Al2 O3 6SiO2 2HCO 3 100 pmc 100 pmc


Chapter 11

In such reactions, the initial 14C concentration of 100 pmc (in pre-1952 samples) is closely maintained, as seen in the examples from Hawaii (Table 11.2). A variety of reactions, of the kinds mentioned and other types, occur in the aerated and saturated zones, causing the initial 14C concentration in pre-bomb groundwaters to vary between 100 pmc (in silicate rocks) and 50 pmc (in carbonate rocks). In reality, the waterrock interaction in carbonate rocks causes a change to only 60 + 5% of the initial 14C in the recharged water. Values of 60 + 5 pmc seem to be common for recent but pre-bomb groundwater in calcareous aquifers (Kroitoru et al., 1987). The initial 14C that typied old groundwater is best assessed by measuring the 14 C in recent local groundwater that is in contact with the same type of rocks. The obtained value can be applied to the age calculation of older water. In the absence of such local information, a drop to 65% of the initial 14 C can be attributed to waterrock interactions in carbonate aquifers, and a drop to 90% of the initial 14C value can be attributed to silicate rocks (plutonic and volcanic rocks, sandstone, and quartzite). Example: A local shallow water has been observed to contain 65 pmc and 5 TU. A sample from an adjacent deep well, in similar rocks, revealed 20 pmc and 0 TU. What is the deduced age of the water in the second well? The value of 65 pmc may be taken as the initial 14C concentration of the groundwater when it rst reached the deep aquifer. The observed 20 pmc represents 20 6 100/65 30.7% of the initial value, indicating an age of 9000 years (Fig. 11.1) The reader is referred to a number of basic articles dealing with chemical and isotopic aspects of groundwater dating by radiocarbon: Back and Hanshaw (1970), Fontes (1983), Geyh (1972, 1980), Pearson and Hanshaw (1970), Pearson and Swarzenski (1974).



C Abundances and Their Relevance to Dating of Groundwater


So far we have discussed the occurrence of 14C in hydrological systems. In a similar way one can follow 13C. Its abundance in rocks, organic material, and groundwater is expressed in permil deviation of the 13C:12C ratio in the sample from that in a standard (PDBa belamnite carbonate from the Pee Dee formation of South Carolina). Most marine carbonate rocks have d13C 2 to 0%, whereas frequent values for organic material and CO2 in soil are 28% to 20%. Most plants have values around 23 + 3%, but certain plants have more positive values, around 12 + 2% (Tables 11.3 11.5 and Figs. 11.6 and 11.7).

Radiocarbon Dating Table 11.3 d13C Values for Selected Samples from Saudi Arabia Source Tuwayq Mountain limestone Upper Dhruma limestone Upper Wasia sandstone Carbonaceous shale, from 241 m Lignite, from 1450 m Thorn plant, living
Source: From Shampine et al. (1979).


d13C (%) 0.8 0.9 1.3 25.7 23.4 24.5

The concentration of d13C in groundwater is determined by the input of recharged water and by reactions with rocks. For example, the reaction of water charged with CO2 of d13C 25% is H2 O CO2 CaCO3 ?Ca2 2HCO 3 d13 C 25% d13 C 0% d13 C 12:5% In contrast, in reactions with silicates, the original (organic) d13C

Table 11.4 Germany Analyses no. H-415 H-414 H-447 H-655 H-680 H-701 H-723 H-703 H-702 H-679 H-749

Carbon Isotopes of Various Samples from a Forest Near Heidelberg, Material Air Co2 Soil Co2 Growing leaves Air CO2 Air CO2 Air CO2 Soil CO2 Growing leaves Growing leaves Humus 02 cm Humus 25 cm Collection date Apr 1958 Apr 1958 Jun 1958 Apr 1959 Jun 1959 Jul 1959 Mar 1959 Apr 1959 Jul 1959 Jun 1959 Jun 1959 d13C (%) 23.8 23.4 29.5 23.8 23 21.8 23 28.1 31.4 25.7 26.0

C (pmc) 109 104 109 123 129 126 106 112 120 94 90

Source: From Vogel (1970).

240 Table 11.5 d13C in Soil CO2 and Associated Plants in Northern Chile Station 1 2 3 d13C (%), soil 14.7 22.3 18.3 d13C (%), plant 14.0 28.1 20.0 to 23.6

Chapter 11

Source: From Fritz et al. (1979).

values will be retained: H2 O 2CO2 2NaAlSi3 O8 ?2Na Al2 O3 6SiO2 2HCO3 d13 C 25% and H2 O CO2 2KAlSi3 O8 ?2K Al2 O3 3SiO2 2HCO 3 d13 C 25% d13 C 25% At this point the d13C data of the Hawaii study (Table 11.2) warrant discussion. The tritium values indicated a pre-1952 age, the 14C values of 85 d13 C 25%

Fig. 11.6 13C histogram in plants from Australia. Two major groups evolve, the total range being from 36% to 10%. (Following Rafter, 1974.)

Radiocarbon Dating


Fig. 11.7 13C histogram in plants from Salar de Atacama, Chile. Two major populations emerge: d13 C 23+3% and d13 C 14+2%, attributed to different systems in plant metabolism. (After Fritz et al., 1979.)

97 pmc indicated no, or little, lowering of the initial 14C value (100 pmc) by interaction with secondary calcite (section 11.4). The corresponding d13C values are 19 to 15%. These values are closer to common plant material (23 + 3%) and far from calcareous rocks (2 to 0%). Thus the 13C changed only slightly due to waterrock interactions in the basaltic aquifers.

11.7 Application of d13C to Correct Observed 14C Values for Changes Caused by Interactions with Carbonate Rocks
It has been suggested by several researchers that d13C values can be applied to evaluate the extent to which 14C in groundwater has been altered by exchange with rocks. Three values have to be known: . . . The d13C value of the local organic soil material, representing the initial composition of groundwater, prior to the reaction with rocks. The d13C value of the local aquifer rocks. The d13C value in the studied groundwater.

For example, if the soil has d13C 24%, the rock 1%, and the water 19%, then the initial 14C in the water was larger (in absolute values) by a factor of 1 24 1:3 1 19 If the 14C in the same water is observed to contain 30 pmc, then this value should be multiplied by 1.3 in order to correct for 14C losses during reaction with aquifer carbonates: 30 6 1.3 39 pmc. This value is then applied to the decay curve (Fig. 11.1), and an age of 7500 years is obtained


Chapter 11

(instead of the 10,000 years indicated by the noncorrected 14C value of 30 pmc). This mode of correcting 14C values for losses through interaction with rocks has serious drawbacks because the composition of 13C in soil materials and aquifer rocks varies over a wide range. It is hard, and occasionally impossible, to collect relevant samples for measurement. In several studies the more common values of 25% for d13C of soil material and 0% for d13C of rock are assumed. However, in certain cases such assumptions lead to severe overcorrecting. For example, in well 2162 at Serowe, Botswana, the 14C content was 95 pmc and the d13C was 11%. Hence, the correction factor would be 0 25 2:3 0 11 Applying this factor to the observed 14C value in the water, a value of 95 6 2.3 219 pmc is obtained. This is clearly a heavy overcorrection (this is not a post-bomb case, as the accompanying tritium was only 0.7 TU). In this example the overcorrection is obvious because it leads to a value that is higher than possible. But if, for example, the observed 14C value were 12 pmc, then such a correction would yield a value of 28 pmc, which is in the permitted range, and hence the overcorrection would not be noticed. The solution in the cited case from Botswana may be that the local plant community was not of the type that has a d13C value of 25%, but a plant type that has a d13C value of 13% (Fig. 11.6). The problem of how to select the right paleo-input values is discussed in Chapter 15, which deals with paleohydrology, paleoclimate, and groundwater dating. As will be discussed later, the main importance of the carbon isotopes in hydrological studies lies in . . . . . Providing relative ages Indicating aquifer ow velocities Checking the continuity of proposed regional aquifers Studying mixed systems Establishing modes of ow

In these applications the d13C and

C values serve as most useful tracers.

Radiocarbon Dating


11.8 Direction of Down-Gradient Flow and Groundwater Age Studied by 14C: Case Studies
Regional aquifers consist, in certain cases, of a recharged outcrop of a conductive rock layer that dips below other rocks and is thus partially conned (section 2.8). Occasionally, wells tap only the conned section of such an aquifer, but in other cases wells also exist in the recharge area. In such systems carbon isotope studies are relevant for . . . Checking the suggested continuity of water ow in the aquifer Checking additional recharge routes Calculating ow velocities

11.8.1 Artesian Aquifer, South Coast of South Africa

An often quoted case study (Vogel, 1970) is that of an artesian aquifer in an area near the south coast of South Africa (Fig. 11.8). The decrease in 14C downslope from the aquifer has been taken by the researcher to indicate continuity. One can even calculate the velocity of groundwater ow in the aquifer by selecting two points on the lines of Fig. 11.8, for example, 2 km 4000 years and 18 km28,000 years. The average ow velocity in the aquifer is 18 2 61000 0:66 m=year 28; 000 4000

Fig. 11.8 14C ages (assuming initial concentration of 85 pmc) of water samples from artesian wells near the south coast of South Africa as a function of the distance from the outcrop of water-bearing strata. (From Vogel, 1970.)


Table 11.6 Hydrological and Isotopic Data of Groundwaters in the Paris Basin
No. 1 2 3 4 5 6 4.0 3.8 2.8 4.7 6 3.6 Southeast 0.3 3.1 5.1 2.4 2.4 Region Place Aquifer Source Stratigraphic unit tapped Date HCO3 (meq/l) Tritium (TU) d13C (%)
14 C (pmc)

13.0 17.7

7 8 9 10 11 12

77 27 9 10 1.d.* 1.d. 1.d 21 1.d. 1.d 1.d.

15.0 12.8



1.d. 1.d. 1.d. 1.d. 7 208 10 1.d. 37 1.d. 1.d. 1.d. 1.d.



13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 West

Parly-Chenons Parly-Bernier Poilly Dracy Chichery Chichery Migennes Migennes Neuilly Fleury Champvallon Grand-Chaumont Froville Appoigny Appoigny Grande Paroisse Montbouy Nuisement Humbecourt Chaudefontaine Voillecomte Montier-en-Der Dompremy Ste Menehoule Barlieu Blancafort Chapelle Angilon Bemecourt Thiberville Brou 2.8 2.4 5.3 4.48 6.8 2.2 5.6 5.2 1.d. 4.7 3.9 4.1 2.8 5.2 3.6

Free Free Free Conned Conned Conned Conned Conned Conned Conned Conned Free Free Conned Conned Conned Conned Free Free Conned Free Conned Conned Conned Conned Conned Conned Conned Conned Conned

Well Spring Spring Drill Drill Drill Drill Drill Artesian Artesian Artesian Well Well Artesian Artesian Artesian Artesian Drill Drill Drill Well Drill Artesian Artesian Drill Drill Drill Drill Drill Drill

Upp. Albian Upp. Albian Mid. Albian Upp. Albian Upp. & Mid. Albian Upp. Albian Upp. Albian Upp. Albian Lower Albian Upp. Albian Cenomanian Chalk Turonian Barremien Barremien Albian Upp. Albian Albian Albian & Aptian Albian & Aptian Albian & Aptian Albian & Aptian Albian Albian & Jurassic Albian & Cenomanien Albian & Cenomanien Rauracian Albian & Kimmeridgian Albian

10/66 10/66 10/66 7/69 7/69 4/66 10/67 7/69 3/69 11/67 3/69 7/69 7/69 3/69 10/67 7/69 10/67 6/69 6/69 6/69 6/69 6/69 6/69 6/69 10/67 10/67 11/67 5/69 5/69 5/69

Chapter 11

13.2 13.0 9.0

94.7 86.7 91.7 66.7 58.0 53.2 46.6 67.3 15.9 14.9 13.6 95.6 72.5 0.6 11.6 3.2 28.9 84.3 76.9 74.8 66.3 52.8 17.9 1.4 82.1 42.2 34.2 75.5 65.3 52.0

Northwest 1.d. 4.9

Radiocarbon Dating

4.9 4.1 4.4 3.2

5.7 9.8 14.2 8.2 9.6 11.4 10.9 10.9

1.d. 12


13.3 2.9 13.2 1.d. 8.5

28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 47 48 49 1.d. 16.3 13.3 10.6 14.3 15.3 15.0 14.1

40.9 37.5 36.9 21.7 15.9 16.0 12.4 12.4 7.2 78.6 1.4 9.7 9.1 8.9


12.2 16.4 95


Chateadun Gauciel Marais-Verniet Vernon Les Logs St. Pierre-en-Port Le Trait Mantes Pont delArche Honeur Incarville Epinay Villeneuve ` Acheres Ivry Orsay Le Pecq Pantin Issy Noisy le Grand Noisy le Grand Paris ORTF Aulnay sous Bois Aulnay sous Bois Aulnay sous Bois ViryChatillion 3.3 3.4 3.0 4.1 5.8 7.5 3.4 2.7 2.9 3.2 3.5 2.6 2.6 2.5 3.1 3.1 2.6 2.9 2.9 2.9 3.1 7.8 7.3 6.4 3.7 3.5 3.7 3.2 2.7 1.0 2.6 2.1

Conned Conned Conned Conned Conned Conned Conned Conned Conned Free Conned Conned Conned Conned Conned Conned Conned Conned Conned Conned Conned Conned Conned Conned Conned Conned

Artesian Drill Well Artesian Drill Artesian Artesian Artesian Artesian Spring Artesian Artesian Drill Drill Drill Drill Drill Drill Drill Artesian Artesian Drill Drill Drill Drill Artesian

Albian Upp. Albian Upp. Albian Albian Albian & Cenomanian Upp. Albian Upp. Albian Upp. Albian Up. Albian Cenomanian Jurassic to Cenomanian Albian Albian Albian Albian Albian Upp. Albian Albian & Barremian Albian Albian Albian Albian Albian Albian Albian Albian

6/69 7/68 7/68 7/68 8/68 8/68 7/68 3/66 11/67 7/68 5/69 3/68 6/67 3/68 1/68 1/68 3/68 12/66 7/69 3/68 8/69 2/67 3/68 3/68 10/69 8/69

*l.d., limit of detection. Source: Extracted from Evin and Vuillaume (1970).



Chapter 11

This case study is a good example for demonstrating the general idea of expected behavior and the application of 14C in aquifer studies. However, more data are needed in such cases: . . . . . Points of sampling (in Fig. 11.8 a gap of 7 km exists between the central wells) Piezometric levels Temperatures Chemical compositions Isotopic compositions (e.g., dD, d18O, d13C, and tritium)

The continuity of the aquifer and active ow in it are independently checked by each of these parameters. This is essential because 14C may decrease with depth (and distance) also in cases of discontinuous ow. As a matter of fact, the obtained average ow velocity of 0.66 m/year is extremely slow, and it might indicate lack of ow in parts of the system.

11.8.2 Paris Basin

A classical hydrochemical study of the Paris basin, 400 km across, has been presented by Evin and Vuillaume (1970). Their data have been compiled in Table 11.6, and the location of studied wells is plotted in Fig. 11.9. Important information included in Table 11.6 relates to the type of aquifer (phreatic or free versus conned), the nature of the water source (spring, well, artesian ow), and the stratigraphic unit at which the respective water was tapped. A hydraulic map of piezometric level contours has been constructed (Fig. 11.10) for water in the Albian aquifer. The distinction of aquifers has to be remembered in the processing of hydrological and hydrochemical data. Too often piezometric level contour maps are prepared of all the wells in a study area, ignoring the stratigraphic position of the sampled water systems. In cases where water is abstracted from aquifers in different stratigraphic units, water level contour maps have to be produced for each aquifer separately (not mixing apples with bananas). The ages applied to draw Fig. 11.11 were calculated by the researchers assuming an initial 14C concentration of 80 pmc. The contours were drawn in 14C half-life intervals. A general aging of water from the recharge areas in the peripheries down-dip in the conned Albian aquifer is seen in Fig. 11.11, supporting the original hypothesis that was based on the piezometric data (Fig. 11.10). The Paris basin study warrants a closer look. In Fig. 11.11 it is seen that the spacing between studied wells was several kilometers near Paris, tens of kilometers in the periphery, and almost 100 km between the southern wells and the central ones. The conclusion that may be drawn is that the

Radiocarbon Dating


Fig. 11.9 Location map of wells studied in the Paris basin; well numbers as in Table 11.6. (From Evin and Vuillaume, 1970.)

aging of water toward the central part of the Albian aquifer should be regarded with extreme caution: many more wells have to be studied and local deviations may be discovered. At this point it might be asked whether a d13C correction should be applied to the 14C values in order to calculate groundwater ages in the Albian aquifer of the Paris basin. To check this point the data for the Albian aquifer (Table 11.6) have been drawn in a d13C14C diagram (Fig. 11.12a). A random scatter is seen, indicating that 14C dilution by interaction with carbonate rocks is not a continuous process along the down-gradient ow in an aquifer. Hence, in the Paris basin no grounds exist for d13C corrections. The tritium-14C values of the Albian aquifer of the Paris basin are drawn in Fig. 11.12b. Carbon-14 values in the free water table samples are in the range of 6696 pmc, with an average of 80 pmc. This range is rather high, and an initial post-bomb 14C of more than 130 pmc must have dominated most recharge waters in the free-water-table aquifer, as may also be deduced from the accompanying post-bomb tritium values. It seems, thus, that immediate reactions with soil and rock carbonate lowered the 14C concentration to a value of about 60% of the recharge concentration. A lower limit to the initial value can be dened by the highest 14C values


Chapter 11

Fig. 11.10 Piezometric levels (in masl) of the Albian aquifer. Recharge seems to occur in the peripheries, giving rise to down-gradient ow toward Paris in the conned Albian aquifer. This hydrological hypothesis has been tested by 14C dating (Fig. 11.11). (Following Evin and Vuillaume, 1970.)

observed in the conned (and tritium devoid) aquifer sample. This value is 58 pmc (sample 5). Thus the initial 14C value in the studied aquifer was around 60 pmc for pre-bomb recharge and 80 pmc for post-bomb recharge. The researchers of the Paris basin selected the 80 pmc value (Fig. 11.11). Four samples (no. 4, the July 1969 sample no. 6, no. 17, and no. 19; Table 11.6) have post-bomb tritium, yet they are from the conned part of the aquifer. Does this necessarily mean rapid ow into the conned aquifer, or is there another explanation? These cases may represent mixed pumping of

Radiocarbon Dating


Fig. 11.11 14C values (in pmc) and iso-14C lines in half-life intervals (assuming an initial 14C content of 80 pmc). 1T: 40 pmc; 2T: 20 pmc; 3T: 10 pmc; 4T: 5 pmc, and 5T: 2.5 pmc. The observed increasing age toward the center of the basin may agree with the hypothesis of continuous ow as postulated by the piezometric map (Fig. 11.10). (From data by Evin and Vuillaume, 1970.)

the conned Albian aquifer with shallow free-table water. The Migennes (no. 6) well revealed the following sets of data: October 1967: O TU and 46.6 pmc July 1969: 21 TU and 67.3 pmc Thus, in the 1969 pumping, evidently post-bomb shallow water was added. These examples demonstrate the importance of tritium measurements in every 14C study. In the Paris basin a relatively large number of tritium measurements were done and, except for the four samples mentioned, no tritium was detected in the samples assigned to the conned aquifer.

11.8.3 Watrak Shedi Basin, Western India

Borole et al. (1979) presented another example of a regional aquifer with 14C ages increasing down-gradient. Figure 11.13 reveals a water table map of the


Chapter 11

Fig. 11.12 13C and tritium as a function of 14C in the Albian aquifer of the Paris basin (Table 11.6). 6, free water table; dots, conned. Initial 14C value is 5880 pmc (see text).

500-km2 subbasin of Watrak Shedi in western India. The upper half of the basin was hypothesized to act as an intake area, feeding a conned aquifer existing in the downow lower half of the basin. Carbon-14 results are given in Fig. 11.14 in terms of apparent radiocarbon age (i.e., an age calculated assuming an initial value of 100 pmc). Thus waters with an initial 14C value of 80 pmc will have an apparent age of 2000 years (Fig. 11.14). The upper, northeast part is dominated by apparent ages of about 2000 years, representing the phreatic part of the aquifer. In the lower, southwest part ages become progressively older, interpreted as reecting the connement of

Radiocarbon Dating


Fig. 11.13 Water-level contours of the Watrak Shedi subbasin, western India (April 1978). A gradient of 0.50.6 m/km is deduced. Down-gradient ow in this 500 km2 basin was hypothesized. (From Borole et al., 1979.)

the aquifer. What is the down-gradient ow velocity in the conned part of the aquifer shown in Fig. 11.14? It seems that the connement begins with the lower edge of the 2000-year apparent age zone. The distance between the lowest 2000-year contour and the 6000-year contour is about 24 km. Hence, the average velocity is 2461000 6 m=year 6000 2000 The apparent age contours in Fig. 11.14 were based on data from shallow (3080 m) wells. A few values for deeper wells are given as well (circles). The age values in these deeper wells are signicantly higher than in the neighboring shallow wells. This was interpreted by the researchers as indicating little or no downward mixing of the subaquifers. A good agreement is thus observed between the hydrological model, based on the water table data (Fig. 11.13) and the observed 14C data (Fig. 11.14). The down-gradient ow in the conned aquifer was further tested by electrical


Chapter 11

Fig. 11.14 Apparent radiocarbon ages (see text) in shallow (dots) and deeper (circles) wells and age contours for the Watrak Shedi subbasin. The 2000-year values correspond to the recharge area (equivalent to an initial 14C of 80 pmc). The higher apparent ages indicate connement of the aquifer in the lower half of the subbasin. A ow velocity of 6 m/year is calculated in the conned aquifer (see text). (From Borole et al., 1979.)

conductivity data (Fig. 11.15). The values indicate fresh water (1000 mmho/ cm) in the phreatic aquifer and gradual salinization in the conned section.

11.9 Flow Discontinuities Between Adjacent Phreatic and Conned Aquifers Indicated by 14C and Other Parameters
Phreatic aquifers are often regarded as recharge zones feeding adjacent conned systems. A continuous through-ow is commonly envisaged, controlled by (and deduced from) water level gradients and transmissivities. However, in certain cases a discontinuity is observed between the phreatic and conned parts of a system, reected in abrupt changes in the chemical

Radiocarbon Dating


Fig. 11.15 Contours of electrical conductivity of groundwaters of the Watrack Shedi subbasin. The phreatic section reveals fresh water values around 1000 mmho/ cm, whereas gradual salinization is observed down-gradient in the conned section. (From Borole et al., 1979.)

and isotopic compositions and, especially, in tritium, 14C, 4He, and other age indicators. Six case studies that reveal phreatic-conned discontinuities are briey discussed below. They were described in detail in Mazor and Kroitoru (1987).

11.9.1 The Judean Mountains, Central Israel

This is an anticlinal structure of marine carbonates of the Judean Group (Cenomanian-Turonian), covered on the anks by chalk and marl of the Mt. Scopus Group (Senonian) (Figs. 11.16 and 11.17). Average annual rainfall on the mountain crest is 550 mm/year, on the Hashphela foothills to the west the value is 450 mm/year, and in the Judean Desert, on the eastern slope, the value drops to 200 mm/year. Limestone, dolomite, and marl beds of the Judean Group are exposed on the mountain crest, acting as the main recharge area and hosting a phreatic groundwater system penetrated by many wells. The Judean Group rocks are covered on the anticlinal anks by chalk and marl of the Mt. Scopus Group. The latter formation hosts limited

254 Fig. 11.16 Study area of the Judean Mountains, central Israel. Limestone and dolomite (Cenomanian-Turonian) outcrops serve as recharge areas into a phreatic aquifer, conned on the anks by younger chalk (Senonian). (From Mazor and Kroitoru, 1987.) Chapter 11

Radiocarbon Dating


Fig. 11.17 Eastwest transects through the Judean Mountains of Judean Group rocks, covered by Mt. Scopus Group rocks. Tritium and 14C values in well samples reveal recent (post-bomb) waters in the phreatic recharge zone and water several thousand years old in the conned zones. The transition is abrupt, indicating that the conned zones are poorly drained. Constancy in d18O values (5.5%) indicates common recharge at the mountain crest rainy area. Constancy of the d13C values (12 + 1%) indicates absence of secondary isotopic exchange reactions, making 14C a reliable tool for dating in this system. (From Mazor and Kroitoru, 1987.)

phreatic water systems of its own, but connes the Judean Group water system. A study (Mazor and Kroitoru, 1987) revealed post-bomb tritium and 14C values in the phreatic Judean Group system, and no tritium and low 14 C in the conned Judean Group system. The transitions are abrupt, both on the western and eastern anks, as seen in Fig. 11.17. Constancy in the dD and d18O data (Fig. 11.17) indicates that the phreatic and conned waters both originate from the same mountain crest


Chapter 11

recharge zone. Thus the phreatic and conned zones seem to communicate hydraulically, but the drainage rate of the conned section seems to be restricted, as indicated by the high 14C ages. The validity of 14C as an age indicator in the described study area has been established by the observed constancy of d13C values (12 + 1%; Fig. 11.17) and of HCO3 and other components. The conned water has calculated ages of several thousand years (Kroitoru et al., 1987).

11.9.2 Bunter Sandstone Aquifer, Eastern England

The Bunter sandstone aquifer has been studied over an area of 2000 km2 in eastern England (Fig. 11.18). A large body of data has been published by Andrews and Lee (1979) and Bath et al. (1979). The regional geology, shown in Fig. 11.19, reveals a sequence of formations from the Permian in the west to the Jurassic in the east, the strata dipping eastward. A more detailed geology of the study area, with sampled well locations, is given in Fig. 11.20, and a cross-section is given in Fig. 11.21. The researchers suggested that water is recharged at the Bunter sandstone outcrops and moves eastward, down-gradient, into a conned section.

Fig. 11.18 Study area of the Bunter sandstone in eastern England: 1area shown in Fig. 11.19; 2area shown in Fig. 11.20. Topographic elevations (masl) are indicated. (Following Mazor and Kroitoru, 1987.)

Radiocarbon Dating


Fig. 11.19 Generalized geological map of a section of east England. (Following Mazor and Kroitoru, 1987.)

The reported data have been plotted in composition diagrams in order to determine whether it is really one continuous aquifer. The Cld18O plot (Fig. 11.22) reveals three data clusters, indicating that three specic water groupsA, B, and Coccur. The Cl14C plot (Fig. 11.23) also reveals three

Fig. 11.20 Geology and location of sampled wells in the study area of Bunter sandstone aquifer. (Following Bath et al., 1979.)


Chapter 11

Fig. 11.21 Suggested geological cross-section of the Bunter sandstone aquifer. The researchers suggested that water recharged in the western outcrops ows eastward down-gradient into the conned section. (Following Bath et al., 1979.)

groups, but the data of group A are spread along a line, interpreted as a mixing line of a recent saline component (possibly contaminated with anthropogenic chlorine) and a several-thousand-year-old, chlorine-poor, end member. The three geochemical groups have a simple geographical distribution pattern of northsouth strips, as seen in Fig. 11.24. Group A coincides with the belt of phreatic Bunter sandstone outcrops, whereas groups B and C are in the conned, east-ward-dipping section. The 14C, Cl, and He data maps of Fig. 11.24 reveal two discontinuity linesI and II. These lines are parallel with the strike of the rock strata and formation contacts (Figs. 11.20 and 11.21). Thus there is little or no active throughow from the phreatic zone of group A to the conned zone of group B.

Fig. 11.22 Cld18O plot of the Bunter sandstone wells. Three distinct geochemical groups emerge: A, B, and C. (Data from Bath et al., 1979.)

Radiocarbon Dating


Fig. 11.23 Cl14C plot of the Bunter sandstone wells. Again, three groups emerge. The group A points plot along a line, interpreted as a mixing line of recent (postbomb, also tritium containing) saline (polluted?) water with several-thousand-yearold fresh water. (Data from Bath et al., 1979.)

Furthermore, a discontinuity also occurs in the conned zone, and the group B section does not communicate freely with the group C section. The Bunter sandstone dD and d18 O data provide further support for the lack of communication between the phreatic and conned aquifer sections. The data plot in Fig. 11.25 along a line, but the data reveal an order of B?A?C. In other words, one is dealing with three distinct water groups, revealing different environmental conditions that prevailed at the time of recharge. The three water groups of the Bunter sandstone have distinct ages, as revealed by two independent age indicators, 14 C and 4 He (Fig. 11.26). The positive 4 He14 C ages correlation gives the age grouping a high degree of condence. From Fig. 11.26 it seems that water group C has for a long time been separated from group B, but the discontinuity between A and B is also maintained in Fig. 11.26. Bearing in mind the concept of stagnant groundwater prevailing beneath the level of the terminal base of drainage (section 2.13), let us have a second look at the geological cross-section of the Bunter sandstone aquifer (Fig. 11.21). The rock strata dip eastward in the direction of the sea, attaining depths of hundreds of meters below sea level. Thus, stagnation is


Chapter 11

Fig. 11.24 14C, He, Cl, and temperature data marked on the well location map (Fig. 11.20). The three distinct geochemical groupsA, B, and Calready dened in Figs. 11.22 and 11.23, have a clear geographical pattern: group A coincides with the phreatic wells in the Bunter sandstone outcrop area, whereas groups B and C are in the conned section. The data mark two discontinuity lines, I and II, discussed in the text. (Data from Bath et al., 1979.)

to be expected and is supported by the discussed chemical and isotopic data. A glance in Fig. 11.18 reveals that the topographic relief of the suggested recharge area is very shallow, only a few tens of meters above sea level. Thus, no extra-high hydraulic pressures can be developed that could push groundwater through theoretical U-tubes in the Bunter sandstone. It seems plausible that the wells of zone A (Figs. 11.2211.26) tap a through-ow system (phreatic aquifer), whereas the wells of zones B and C tap stagnant systems (fully conned aquifers).

Radiocarbon Dating


Fig. 11.25 dDd18O plot of the Bunter sandstone wells. The obtained pattern is discussed in the text. (Data from Bath et al., 1979.)

11.9.3 Lincolnshire Limestone Jurassic Aquifer, Eastern England

The Lincolnshire limestone Jurassic aquifer in eastern England provides another insight into a phreatic-conned system. Isotopic data were reported (Dowing et al., 1977) from a number of wells in this system, located in the

Fig. 11.26 4He concentrations relative to 14C ages of waters in the Bunter sandstone wells. 14C ages were calculated from the data of Bath et al. (1979), applying 70 pmc as an initial 14C concentration. The positive correlation validates the relative dating by the two independent methods. Waters of groups A, B, and C have been recharged at different times and do not represent continuous down-gradient ow (see text).


Chapter 11

Fig. 11.27 Set of 14C data (pmc) marked on well locations in the Lincolnshire limestone aquifer. The arrow depicts the orginally suggested direction of groundwater ow. Dashed line marks discontinuity between phreatic (A) and conned (B) aquifers. (Data from Dowing et al., 1977.)

intake area and in part of the conned westward-inclined section. A distinct discontinuity (dashed line) is observed in 14 C (Fig. 11.27), supported by four other parameters: tritium, d13 C; dD, and d18 O. Thus little or no hydraulic communication takes place between the phreatic and conned sections of the described Lincolnshire limestone aquifer.

11.9.4 Gwandu Formation, Sokoto Basin, Northern Nigeria

This system has been studied by Geyh and Wirth (1980). Figure 11.28 depicts the outcrop areas and the suggested groundwater ow direction. The 14 C data reveal a sharp discontinuity of waters, with 3270 pmc near the outcrops (A) and 27 pmc in the downow section of the conned aquifer (B)another example of lack of hydraulic communication between adjacent phreatic and conned systems.

11.9.5 The Florida Limestone Aquifer

This system provides another example of a phreatic-conned interrelationship. Data are given in Table 11.7. A clear phreatic-conned discontinuity is established by 14 C; d13 C, and tritium.

Radiocarbon Dating Table 11.7 Isotope Data for Wells in the Florida Limestone Aquifer Well Weeki Vachee Lecanto #5 Lecanto #6 Frost proof Holopane Arcadia
14 C (pmc)


d13C (%) 13.7 11.5 11.8 9.8 9.6 8.3

Tritium (TU) 103 + 10 36 + 4 15 + 1 0+1 1+1 0+1

Remarks Recharge zone Recharge zone Recharge zone Conned zone Conned zone Conned zone

62.4 50.0 51.1 6.7 5.2 3.0

Source: From Pearson and Hanshaw (1970).

11.9.6 The Blumau Aquifer, Southeastern Austria

This complex has been intensively studied (Andrews et al., 1984). Drastic discontinuities were reported for groundwater properties passing from the phreatic part of the aquifer to the conned part. The transition is observed between two wells, about 400 m apart. For example, 14 C drops from 114 pmc to 48 pmc, tritium drops from 49 TU to 0.8 TU, d18 O drops from 8.6% to 9.3%, and bicarbonate rises from 100 mg/l to 320 mg/l.

Fig. 11.28 14C values (pmc) in wells of the Sokoto basin, northern Nigeria. The arrow denotes the orginally suggested groundwater ow direction. The phreatic aquifer (A) coincides with the rock outcrops (stippled) and has high 14C values. An abrupt drop in 14C values is observed in the adjacent conned section of the system (B). (Data from Geyh and Wirth, 1980.)


Chapter 11

11.9.7 Conclusions Drawn from the Case Studies

The examples of phreatic-conned discontinuities shed light on a number of basic hydrological features: . Flow velocities of water in an aquifer, calculated by gradients and transmissivities, provide the maximum possible values. These are subject to limitations imposed by stagnation conditions. In extreme cases, conned systems may be rich in fossil karstic conduits, but with no through-ow due to complete connement and/or burial beneath the level of the terminal base of drainage. Restricted drainage may, in certain cases, explain discrepancies between hydrologically calculated ages, using gradients and transmissivities, and much higher ages obtained from isotopic age indicators such as 14C, 4He, or 36Cl. In fact, such discrepancies might be used as indicators of poor drainage of partially or completely conned systems. Phreatic systems that do not drain into adjacent conned sections must have their own outputs to maintain the observed young groundwater ages. These outputs have to be identied to gain a full understanding of the regional hydrology. Of special interest is the degree of abruptness of the discontinuities. These may be enhanced by clogging of rock pores in the transition zone. In other cases, a geological barrier may be present, coinciding with a suggested phreatic-conned boundary.

11.10 Mixing of Groundwaters Revealed by Joint Interpretation of Tritium and 14C Data
Mixing of groundwater was discussed in sections 6.6 and 6.7. There, mixing patterns were recognized by processing data from numerous samples (Figs. 6.6, 6.9, 6.17, and 6.18). Mixing may also be recognized from data obtained from a single samplein cases of forbidden combinations of tritium and 14C data. Example: 1.2 TU and 48.3 pmc were found in well 1572, Hanahai, Botswana. What is the age of this water? The values represent a forbidden combination: 1.2 TU indicates pre-bomb (an age of a few decades), whereas 48.3 pmc indicates water a few thousand years old. In other words, the tritium and 14C ages are discordant (disagreeing), and neither is correct. The combination could be formed only by intermixing of old water (zero tritium and < 48.3 pmc) with recent water (post-bomb tritium and post-bomb 14C). This example is of great importance. Concordant ages (agreeing ages)

Radiocarbon Dating


conrm each other, and discordant ages indicate mixing of water of different ages. In the identication of intermixing water types and the calculation of mixing percentages, 14C is useful because it is often the only parameter that occurs in a linear negative correlation with other parameters needed to extrapolate end member properties (section 6.7). Deep groundwaters commonly have high parametric values: high dissolved ion concentrations and elevated temperatures (as compared to the intermixing shallow and cold end member). However, 14C is commonly low in the deep end member (which is old) and is high in the shallow end member (which is young), thus providing the needed negative correlations. Tritium can be used in the same way (section 10.6), but its use is limited to mixtures of old water with postbomb water. If the young end member is pre-1952, it contains no measurable tritium but high concentrations of 14C, making the latter useful in studying mixed waters. An example of the use of 14C in studying a mixed groundwater system is provided by the Hammat Gader spring complex in the Jordan Rift Valley, southeast of the Tiberias Sea (Table 11.8). Four springs emerge at Hammat Gader along a stretch of a few hundred meters. Various parameters have been plotted on compositional diagrams as a function of Cl concentration (Fig. 11.29). Linear positive correlations are exhibited by Li, K, Na, Mg, Ca, Sr, SO4, and Br. These positive linear correlations indicate mixing of a fresh water with a more saline water. Positive correlations with chlorine were observed for three additional parameters: temperature, dissolved helium, and radium, (Fig. 11.30). A negative correlation was provided in the Hammat Gader study by 14C alone (Fig. 11.31). The vertical axis in Fig. 11.31 deserves some discussion: the 14C data (reported in pmc) provide

Table 11.8 Dissolved Ions (mg/l) in Springs AD, Hammat Gader, and Extrapolated Fresh (fem) and Saline (sem) End Members Spring sem A B C D fem Li 0.23 0.143 0.079 0.057 0.010 0.0 Sr 17 10.4 6.0 4.1 1.3 0.0 K 33 21.8 13.1 10.5 3.9 0.9 Na 375 245 140 120 55 18 Mg 48 39.8 44.5 37.5 32.7 34 Ca 196 152 105 124 89 78 Br 8.8 5.4 3.7 2 0.0 Cl 800 506 300 218 87 10 SO4 262 177 121 100 58 37 HCO3 272 330 344 361 381 385

Source: From Mazor et al. (1973).


Chapter 11

Fig. 11.29 Composition diagrams of four springs issuing a few hundred meters apart at Hammat Gader, Jordan Rift Valley, Israel. The mixing of two water types is evident. (From Mazor et al., 1980.)

the value of the 14C:12C ratio in the sample, compared to a standard (section 11.2). In the hydrochemical jargon the pmc values are often called 14C concentrations. However, to obtain values that are really concentration related, the pmc value has to be multiplied by the corresponding HCO3 concentration, as shown in Fig. 11.31. The best-t line is seen in Fig. 11.31 to extrapolate to 69 8C, providing the maximum possible temperature of the warm end member. The real temperature of the warm end member lies in the range of the highest temperature measured (52 8C) and the extrapolated value (69 8C). The extrapolated temperature of the cold end member was obtained from Fig. 11.30, assuming a chlorine concentration as low as that of local rainwater, 10 mg/l. An extrapolated temperature of 25 8C was obtained for the cold end member. The real value lies between this extrapolated value of 25 8C and the lowest measured value, 29 8C. The extrapolated chlorine values could then be applied to the positive correlation lines of Fig. 11.29 to calculate the concentration of the dissolved ions in the two end members.

Radiocarbon Dating


Fig. 11.30 Temperature, helium, and radium as a function of chlorine at Hammat Gader, springs AD, and extrapolated end members (see text). (From Mazor et al., 1973.)

11.11 Piston Flow Versus Karstic Flow Revealed by 14 C Data

In piston ow, groundwater is layered in the saturated zone of the intake area, younger water layers over older water layers. Such systems provide


Chapter 11

Fig. 11.31 14C versus temperature in the spring complex of Hammat Gader. The negative correlation could be used to extrapolate to 0 pmc, obtaining a value of 69 8C. The real hot end member lies between the highest value measured (52 8C) and the extrapolated value (69 8C). (From Mazor et al., 1973.)

downward decreasing 14C values in depth proles. In contrast, in a karstic system of water descending in conduits crossing porous rocks, occasionally disordered depth proles occur, with water of relatively high 14C values encountered beneath water with lower 14C values. Case studies near Nyirseg, in eastern Hungary, provide examples for the discussed types of depth proles (Table 11.9). The rst two wells, of Fehergyarmat and Nyirlugos, reveal normal depth proles, with 14C decreasing downward, indicating water layering, which in turn indicates a piston ow of recharged water. The remaining ve wells reveal disordered depth proles, for example, Berettyoujfalu, which has in a sequence of depth prole samples the following 14C values: 85.1, 1.2, and 15.6 pmc. These ve wells encountered karstic conduits or zones of preferred conductivity with waters of varying 14C values. For a review of other methods that have been developed to date ground-waters, the reader is referred to an article by Davis and Bentley (1982).

11.12 Sample Collection for 14C and 13C Analyses and Contact with Relevant Laboratories
Carbon-14 is measured in specialized radioactive counting laboratories and in acceleratormass spectrometer laboratories. In the rst case, relatively large water samples of about 100 l have to be treated, and in the latter case

Radiocarbon Dating Table 11.9 Location Fehergyarmat


Carbon-14 Depth Proles in Wells Near Nyirseg, Eastern Hungary Perforation (m under surface) 7 10 41 56 81 96 < 10 31 34 110 175 < 10 46 73 161 193 229 268 297 313 < 10 55 61 127 133 172 219 70 93 138 181 160 190 154 159 233 253 < 10 131 137 296 355 d13C (% PDB) 15.3 16.1 17.4 12.9 13.8 15.1 17.2 3.1 13.7 13.2 13.0 13.5 15.3 13.1 13.2 14.5 15.6 12.7 14.9 13.5 15.2 22.6 20.7 Tritium (TU) <6 150 <6 119 <6

C + s (pmc) 78.7 + 6.3 12.8 + 1.2 12.1 + 0.9 57.9 + 1.0 27.6 + 1.1 24.9 + 1.1 91.2 + 4.2 54.7 + 3.1 14.0 + 0.8 16.3 + 0.6 22.6 + 0.5 72.3 + 3.1 23.6 + 2.3 16.4 + 0.9 1.8 + 1.8 3.4 + 1.3 8.0 + 0.5 12.6 + 1.2 4.5 + 0.9 7.9 + 1.4 85.1 + 2.4 1.2 + 0.5 15.6 + 2.2




240 <6


Derecske Berettyoujfalu


Source: From Deak (1979).

samples of about 1 1 are sufcient. There is a difference in the price, and each researcher has to determine the track to follow. The larger samples can be reduced by precipitation of the dissolved carbon-containing compounds (mainly HCO3) in the eld, a process that needs some expertise. In any case, care has to be taken to avoid exchange with atmospheric CO2. Carbon-13 is measured mass spectrometrically, either on the sample collected for the radiocarbon or on separately collected samples. You should get your sampling instructions from the laboratory that will conduct the measurements.


Chapter 11

11.13 Summary Exercises

Exercise 11.1: What is the age of water with 25 TU and 102 pmc? Exercise 11.2: What can be said of water in which 0 TU and 70 pmc have been detected? Exercise 11.3: When was water with 0 TU and 0 pmc recharged? Exercise 11.4: Is there something special in groundwater that contains 6 TU and 6 pmc? Exercise 11.5: Based on the data provided in Table 11.6 for groundwaters in the Paris basin, give your expert opinion on the hydrology of well 1, ParlyChenons. Exercise 11.6: Well 6, Migennes, is reported in Table 11.6 as being conned. Check this conclusion in light of the given data. Exercise 11.7: Assess the hydrology of well 19, Montier-en-Der, in light of the data given in Table 11.6. Exercise 11.8: Assess the age of the water in well 47, Issy, applying the data given in Table 11.6. Exercise 11.9: Compare Fig. 11.3 with Fig. 11.12. What is the common thread?


12.1 The Radioactive Isotope of Chlorine and Its Production

Chlorine has three isotopes in nature: 35Clcommon and stable; 36Clvery rare and radioactive, with a 301,000-year half-life; and 37Clless common and stable. Chlorine-36 concentrations are commonly expressed in units of 107 atoms/l of water. The measurement is performed in specialized laboratories with dedicated accelerators. Measurements can be done on 1 1 water samples. A few background remarks on the formation of 36Cl are needed, the reader being referred to a historical discussion by Bentley et al. (1986c). Chlorine-36 is constantly formed by cosmic rays interacting with the atmosphere, and it is incorporated along with stable atmospheric chlorine (mainly sea-derived and airborne) into the hydrological cycle. In addition to the atmospheric source, 36Cl is also formed by in situ reactions in rocks, its production rate being proportional to the uranium, thorium, and chlorine concentrations prevailing in the rocks. Chlorine-36 has also been introduced into the atmosphere by nuclear bomb testing. The major portion of 36Cl is atmospheric, the in situ production amounts to a few percent of the atmospheric contribution, and nuclear bomb testing added a few tenths of a percent.



Chapter 12

12.2 A Potential Tool for Groundwater Dating

Every radioactive isotope detected in groundwater serves as a potential tool for dating. The half-life of 36Cl 3 6 105 yearsis especially promising because it lls in a most important time span, that is, beyond the limits of groundwater dating by radiocarbon. Figure 12.1 depicts a 36Cl decay curve by plotting P36 versus time. P36 is the percent of atmospheric 36Cl left in the sample, which is the parameter measured in groundwater investigations. The time is indicated in half-lives and translated into years before present by multiplying by the 36Cl half-life. In a straightforward mode, one may read from the decay curve the groundwater age that corresponds to a given P36. But there is a long list of complications that have to be overcome, as discussed in the following sections. The literature on 36Cl groundwater dating evolved quickly in the last decade, and a variety of data presentation and interpretation approaches have been applied. In this chapter a simple approach is presented (Mazor, 1992b) in order to provide a clear overall picture, equipping the eld hydrologist with a most important semiquantitative dating tool.

Fig. 12.1 A radioactive decay curve of 36Cl. P36 is the percentage of atmospheric 36 Cl left in the sample. The time axis is expressed in half-lives and in 105-year units. The marked point of 56% P36, taken from the Lachlan case study, reveals water with an age of about 290,000 years. The mode of dening the P36 is explained in later sections.

Chlorine-36 Dating


12.3 Processes Controlling the Groundwater

Cl Concentration in

12.3.1 Geographical Variations in the Production of Atmospheric 36Cl

The ux of cosmic rays varies with sunspot activity and other parameters, and the ux reaching the Earths surface varies with latitude and altitude. Furthermore, reactions with 35Cl produce some 36Cl, which causes a dependence in the distance from the ocean. Altogether, the production of 36 Cl varies spatially by a factor of up to ve. Hence, the 36Cl production rate is site specic and has to be determined for each study site, as outlined later.

12.3.2 Evapotranspiration Affecting the Cl and 36Cl Concentration in Recharged Groundwater

Evaporation and plant transpiration operate on water prior to its arrival in recharged groundwater systems. Evapotranspiration returns part of the precipitated water into the atmosphere, while the dissolved salts, including chlorine, stay behind and become enriched in the water fraction that reaches the ground-water systems. Figure 12.2 shows chlorine and bromine concentrations observed in various wells in a stretch of several hundred square kilometers in the at Murray-Malee region of Australia. Several

Fig. 12.2 Bromide as a function of chlorine in unconned wells of the MurrayMalee region, Australia. The observed positive linear correlation and the fact that the sea value (x) falls on the same line lead to several conclusions that are discussed in the text in the context of groundwater dating by 36Cl. (Following Mazor, 1992.)


Chapter 12

conclusions can be drawn from the observed linear positive correlation and from the fact that the marine value (Cl:Br 293) ts the correlation line: (1) both chlorine and bromine are atmospheric (i.e., sea derived and airborne); (2) the formation of sea spray and its atmospheric transportation do not involve elemental fractionation; (3) chlorine and bromine reveal a conservative hydrochemical behavior, as is well established worldwide (Mazor and George, 1992; Mazor et al., 1992); (4) the concentration of these ions is controlled by a process that acts on both in the same mode, this process being evapotranspiration; (5) the range of several orders of magnitude of observed ion concentration reveals frequent differences in the surface conditions, resulting in different concentrations of chlorine in groundwaters. Similar chlorinebromine correlations have been observed in groundwaters all over the world, indicating the widespread nature of the discussed processes. Evapotranspiration affects 36Cl and stable Cl in the same way. Thus the initial concentration of 36Cl in groundwater must vary locally, in the mode observed for Cl in Fig. 12.2. This leads, in turn, to the conclusion that the initial 36Cl concentration in newly recharged groundwater is site specic and has to be determined for each study site, as is outlined later.

12.3.3 Halite Dissolution

To overcome the large effect of evapotranspiration on the initial 36Cl concentration in recharged water, several researchers applied the 36Cl:Cl ratio in their dating process. The production rates by the different processes and the measurement in the sample were expressed in 36Cl:Cl ratios (Bentley et al., 1986). This procedure ran into difculties because of possible dissolution of halite. Halite (NaCl) occurs occasionally in sequences of old rocks and contains no atmospheric 36Cl. Thus dissolution of old halite produces water with lower 36Cl:Cl ratios, leading to the computation of apparent too old water ages. This obstacle can be overcome by plotting the chlorine data versus bromine (e.g., Fig. 12.2)the Cl:Br ratio in seawater and airborne sea spray is 290, whereas in halite it is over 3000 (section 6.14), hence samples that plot on a line that contains the marine Cl:Br value are freed from the possible involvement of old halite dissolution, and their data can be applied to age calculations.

12.3.4 In Situ Formation of



Two opposing processes control the concentration of 36Cl as a function of the age of the water: the initial atmospheric 36Cl decays, whereas in situ produced 36Cl accumulates. The in situ production of 36Cl varies with rock composition and is thus another site-specic parameter. In old ground-

Chlorine-36 Dating


waters, with ages of 106 years or more, the in situ produced 36Cl reaches a steady state at which the rate of production equals the rate of radioactive decay. The steady-state in situ production of 36Cl places an upper limit of about 106 years on the range of water dating via 36Cl. In other words, in cases of low 36Cl concentration one cannot establish whether any of the original atmospheric 36Cl is left or all the observed 36Cl stems from in situ production. Whenever a small 36Cl concentration is measured in a water sample, the age can still be calculated via the decay graph (Fig. 12.1), but this will be a minimum age and the real age may be signicantly older.

12.3.5 Nuclear Bomb



Along with tritium and 14C, 36Cl has been released into the atmosphere by nuclear bomb testing, increasing the concentration in newly recharged water by up to a few tenths of a percent. This anthropogenic 36Cl does not interfere with groundwater dating, since the 36Cl method can be applied only to waters that are over 104 years old, that is, pre-bomb. Water that is free from measurable tritium and/or contains 14C in concentrations that are lower than the initial 14C concentrationfor example, > 50 pmc (see Chapter 11)do not contain bomb 36Cl.

12.4 Groundwater Dating by


Cl Cl:Cl Ratio in Local

12.4.1 Establishing the Initial Groundwater


As in the case of 3H and 14C, the application of 36Cl for groundwater dating is based on the knowledge of the input values at age zero. In the cases of 3H and 14C, research efforts were directed to the establishment of the concentrations in precipitation. In the case of 36Cl, the concentration varies appreciably at different altitudes and latitudes, and is signicantly increased by evapotranspiration. Hence, the input values have to be established for the water as it entered the aquifer. This is best done by selecting several local springs or wells that comply with the following requirements: . . Waters that are clean of bomb 36Cl contributions. The best criterion for this requirement is that no 3H or other manmade contamination is found in signicant concentrations (< 1 TU). Groundwater samples that are recent in terms of the half-life of 36 Cl (i.e., 36Cl decay being negligible). Samples that comply with this criterion are best selected with the aid of 14C measurements. They should be lower than pre-bomb concentrations in ground-


Chapter 12

water (> 60 pmc), but still signicantly above the limit of the 14C dating method (> 20 pmc). There should be good representation of local recent groundwaters, for example, the full spectrum of salinity, chemical composition groups, and temperatures.

The selected recent water samples should be analyzed for the listed parameters, and the data should be plotted on composition diagrams as functions of the chlorine concentration. The chlorinebromine diagram will serve to select water samples that have marine 36Cl:Cl ratios (ensuring no ancient halite was dissolved). The line observed on the 36ClCl diagram serves as the local intake line (demonstrated later in Fig. 12.7 for the Lachlan Fan case study).

12.4.2 Groundwater Age Read from Isochrones on a 36 CCl Diagram

Figure 12.3 is a schematic version of a 36ClCl diagram of data obtained in eld studies. The local intake line is traced to the zero values through the data points of the selected local recent waters. The data of the recent waters may be spread along an oblique line in the case of regions where evapotranspiration varies from one surface cell to the other, or the data may cluster, revealing uniform and possibly low evapotranspiration effects. At the second stage, isochrone lines can be plotted by half-lives. The age of a water sample can be read directly. For example, sample A in Fig. 12.3 has

Fig. 12.3 Isochrones plotted on a 36ClCl composition diagram. Calculation of the age for samples A and B is discussed in the text.

Chlorine-36 Dating


an (semiquantitative) age of 3 6 105 years, and sample B, which lies in the range of the in situ 36Cl production, has a minimum age of 106 years.

12.4.3 Calculation of P36 and Its Application to Estimate Groundwater Age

The percentage of

Cl left in a sample (P36) equals

P36 % 36 Clmeasured =36 Clinput 6100 A local intake line (from the case study of Lachlan, Australia) is drawn in Fig. 12.4, along with point X, representing a sample that was found to contain 530 6 107 atoms 36Cl/l, accompanied by 3180 mg Cl/l. The corresponding point Y on the local intake line reveals the initial 36Cl input value of 950 6 107 atoms/l. Hence, P36 (530/950) 6 100 55.8%. Applying this value to the decay curve of Fig. 12.1, point O is obtained, and an age of 2.9 6 105 years is read on the lower scale of the horizontal axis.

12.5 A Number of Case Studies

Following are a number of case studies examined in the light of the previous discussion. The reader is encouraged to read the original articles to become familiar with the mode of data processing and interpretation presented by the various researchers.

Fig. 12.4 Mode of calculating P36, the percentage of 36Cl left in the sample, demonstrated for a case discussed in the text (site C, the Lachlan Fan, Australia).


Chapter 12

12.5.1 The Lachlan Fan, Australia

Bird et al. (1989) and Calf et al. (1988) reported a set of 36Cl and Cl data from the Lachlan Fan, southern Australia (Figs. 12.5 and 12.6). The distribution of the 36Cl data is seen in Fig. 12.6 to be uneven; for example, a well with 12 6 107 atoms/l is located near a well with 114 6 107 atoms/l in location A, or a well with 530 6 107 atoms/l is seen near a well with 1175 6 107 atoms/l in location C. The chlorine values reveal a similar distribution. Observations of this nature indicate that the groundwater system in the study area is composed of a number of groundwater cells, or compartments, that have little lateral hydraulic interconnectionan expected phenomenon in at terrains. The data from location A are plotted in Fig. 12.7, and the perfect correlation line of these fresh waters is regarded as representing the local intake line. The spread of the points along the intake line reects degrees of water removal by evapotranspiration prior to recharge into the groundwater system. The complete set of data from the Lachlan Fan region is plotted in Fig. 12.8, along with the intake line, extrapolated from Fig. 12.7. The data of the more saline samples fall below the intake line, indicating a rather old age. The age calculation for one well in location C has shown these waters to be around 290,000 years old (around 1 half-life; Figs. 12.4 and 12.1).

12.5.2 The Murray-Malee Region, South Australia

Calf et al. (1988) and Davie et al. (1989) presented data from the Malee region in the Murray Basin, southern Australia (Figs. 12.5 and 12.9). The data reveal again the existence of groundwater compartments with distinct compositions: (1) a 36Cl value of 9 6 107 atoms/l at the southern edge of the

Fig. 12.5 Key map of case studies from Australia discussed in this chapter: 1 Lachlan Fan; 2Murray-Malee Basin; 3Great Artesian Basin.

Chlorine-36 Dating


Fig. 12.6 Map of a study in the Lachlan Fan, providing sampling points and 36C concentrations in units of 107 atoms/l. The letters designate sampling sites marked in the following gures and are discussed in the text. [Figs. 12.612.10 are based on data published by Bird et al. (1989) and Calf et al. (1988), and processed in Mazor (1992)].

study area is followed to the north by a value of 21 6 107 atoms/l; (2) a value of 28 6 107 atoms/l is seen near a value of 145 6 107 atoms/l at the northern end of Fig. 12.9. A local intake line is drawn through the data points plotted on a 36Cl Cl diagram (Fig. 12.10), applying the Murray group unconned water samples. One Renmark group sample and two of the discharge area samples of the Murray group also lie on the local intake line in Fig. 12.10. These wells thus seem to belong to the presently active unconned system. Other

Fig. 12.7 The 36ClCl diagram for data from location A of the Lachlan case study. The waters at this site are seen to be fresh, as reected by the low chlorine concentrations. The observed perfect correlation line is suggested to represent the local intake line.


Chapter 12

Fig. 12.8 Chlorine-36 as a function of chlorine for the Lachlan case study. The intake line is based on the fresh water samples from location A (Fig. 12.7). All the data points, except one, lie on or beneath the local intake line, indicating ages on the order of one half-life, that is, about 300,000 years (see text). The single point above the intake line may indicate contributions of bomb 36Cl.

Fig. 12.9 Sampling points and Malee study.


Cl concentrations (107 atoms/l) for the Murray-

Chlorine-36 Dating


Fig. 12.10 Chlorine-36 as a function of chlorine for the Murray-Malee study. Symbols designate the reported formation from which the water was sampled: Murray group (), Murray group at discharge areas (squares), Renmark group (circles), Pliocene aquifer (triangle). The local intake line was based on unconned water samples. The data fall on this line or beneath it, indicating old ages.

samples plot beneath the local intake line, indicating groundwaters with high ages.

12.5.3 The Great Artesian Basin

Bentley et al. (1986a) presented a pioneering study of 36Cl in the Great Artesian Basin (GAB) in eastern Australia (Fig. 12.5). The 36Cl data are plotted in Fig. 12.11, along with the Cl, Ca, and SO4 data. Two distinct groups of values are seen in the 36Cl map: a group of wells in the northeast corner of the study area, at the mountainous Great Dividing Range (GDR), contains (1742) 6 107 atoms/l, whereas the conned artesian wells of the GAB contain only (15) 6 107 atoms/l. The rst group of samples was collected from the active recharge area, whereas the second group of samples was collected from artesian wells drilled up to 1800 m into the conned Jurassic (J) aquifer. The dashed line DD marks the abrupt discontinuity inferred from the 36Cl data (Mazor, 1992). A similar pattern is seen in the distribution of the Ca and SO4 concentrations (Fig. 12.11): the values of the conned J aquifer of the GAB are an order of magnitude lower than the values found in the unconned aquifer of the GDR. The distinction is less clear for the chlorine distribution, the higher values in the GDR wells possibly reecting anthropogenic chlorine pollution of the unconned system. The abrupt


Chapter 12

Fig. 12.11 Sample locations in the Great Artesian Basin and concentrations of 36Cl (107 atoms/1) (data from Bentley et al., 1986a), and Cl, Ca, and SO4 (mg/l) (data from Water Resources Commission of Queensland). Line DD marks a discontinuity between the 36Cl, Ca, and SO4 results from unconned wells in the Great Dividing Range recharge area (located at the northeast corner) and the results from the buried conned J aquifer of the GAB.

decrease of 36Cl, Ca, and SO4, and in some of the locations also of Cl, indicates that the unconned groundwater system of the GDR does not communicate with the buried J aquifer. The GDR system may, however, be hydraulically interconnected with the shallow groundwater system of the eastern part of the GAB. The 36ClCl diagram of the GAB (Fig. 12.12) is a ne summary of 36Cl dating. The data of the GDR unconned groundwaters and those of the conned J aquifer of the GAB plot in two distinct locations. The GDR data spread along a line that indicates variability in evapotranspiration water losses prior to recharge at distinct surface cells. A suggested intake line has been drawn through the unconned groundwaters and the origin of the axes. Its location could not be selected precisely because there were no tritium data available to identify wells with bomb contributions (one well at the top of the diagram clearly has a bomb component). The conned GAB groundwaters reveal the same large range of chlorine concentrations, but all are low in 36Cl. This is interpreted as indicating that all the conned waters

Chlorine-36 Dating


Fig. 12.12 The 36ClCl diagram of the GAB study. The local intake line and the in situ production zone are discussed in the text, along with the conclusion that the artesian groundwaters of the Jurassic rock system are 5 106 years old. (Following Mazor, 1992.)

are very old, and the bulk of the observed 36Cl is produced in situ. Thus the conned waters are of an age that is beyond the limit of the 36Cl dating method, that is, > 106 years. This high age is of direct bearing to the question of the nature of the J aquiferwhether the artesian waters are part of a basin-wide through-ow system, as portrayed in Fig. 2.21, or whether they are composed of a multitude of hydraulically isolated compartments that are pressurized by compaction (section 2.14). The 36Cl content of the conned waters, studied in the GAB, is at the limit of the dating method, which is 1 million years. This leaves open the possibility that the real age is much higher and other dating methods are needed to check this point. High groundwater ages support the isolated compartment model and rule out the through-ow model.

12.5.4 The Milk River Aquifer, Alberta, Canada

Bentley et al. (1986b) and Phillips et al. (1986) published 36Cl and Cl data for the Milk River Aquifer in southern Alberta (Fig. 12.13). The 36Cl data are plotted in Fig. 12.14. A group of wells in the southwest corner of Fig. 12.14 has 36Cl values of (2350) 6 107 atoms/l, two wells in the northeast corner have (1315) 6 107 atoms/l, and the central part contains


Chapter 12

Fig. 12.13

Location of the Milk River study area in Canada.

water with only (28) 6 107 atoms/l. Thus different water groups seem to be tapped by the wells, and no lateral ow across the entire study area is indicated by the 36Cl data. The Milk River data are plotted in Fig. 12.15 on a 36ClCl diagram. A number of samples with low Cl concentrations reveal rather high 36Cl concentrations. They seem to belong to recently recharged unconned waters, but they do not trace a local intake line, since the high 36Cl values may reect bomb contributions. The rest of the data occupy a band of signicantly low 36Cl concentrations (6 6 107 atoms/l). By analogy with the GAB study (Fig. 12.12), it seems that here too one deals with old conned groundwaters with an age on the order of 5 0.5 6 106 years. These groundwaters were exposed to varying degrees of evapotranspiration prior to their being recharged.

Fig. 12.14 Sample locations and 36Cl concentrations (107 atoms/l) for the Milk River study. Geographical groups of concentration values indicate that several distinct water types are involved (see text). (Data from Phillips et al., 1986.)

Chlorine-36 Dating


Fig. 12.15 The data of the Milk River study plotted on a (Following Mazor, 1992.)


ClCl diagram.

12.6 Summary
Chlorine-36 is an isotope that can be measured by specialized laboratories and its sample collection in the eld is simple. It is a radioactive isotope with a half-life of 3 6 105 years, making it useful for groundwater age determinations in the range of 105106 years. No conclusions can be drawn on the basis of 36Cl determinations aloneauxiliary data are needed, such as general chemistry, including Cl, Br, as well as tritium and 14C. Samples have to be demonstrated to represent a single water type and not a last-minute mixture of two or more waters (sections 6.6 and 6.7). The local intake line, that is, the local 36Cl:Cl ratio, has to be determined on local samples that are relatively young, but pre-bomb. The age determination has to be regarded as semiquantitative, but its value cannot be overestimated in striving to understand groundwater systems scientically and in relation the pollution aspects. Groundwater older than 105106 years is most probably stagnant, and in any case it is not renewed, but it is isolated from the surface and thus immune to anthropogenic pollution.


Chapter 12

12.7 Summary Exercises

Exercise 12.1: What is the age of a groundwater sample that contains 20% of the initial atmospheric 36Cl? Exercise 12.2: In the center of Fig. 12.10 is a sample marked Renmark G. What is its 36Cl concentration? What was its initial 36Cl concentration? What is the respective P36? What is the age? Exercise 12.3: A water sample is found to have a P36 of 25%. How many half-lives have passed since its recharge? What is the age of this water? Exercise 12.4: The points on Fig. 12.7 lie on the intake line. Thus all these water samples have a recent age. What could be the reason why they do not cluster around a single point? Exercise 12.5: Chlorine-36 measurements are a highly recommended parameter of groundwater studies, especially if conned systems are possibly included. Which other parameters have to be measured in order to establish 36Cl-based water ages? Exercise 12.6: Which sampling strategy will you recommend if a study area includes 70 wells but the budget is enough for only 25 full laboratory analyses?


13.1 Rare, Inert, or Noble?

Helium, neon, argon, krypton, and xenon occupy a special place in the periodic tabletheir outer shell of electrons is complete (2, 8, or 18) and therefore they do not interact with other atoms (section 5.4). This property gives these elements the name inert or noble. They are gases, and they are present in small quantities in air (Table 13.1); hence, they are also called rare gases. It has been pointed out that one of them, argon, is present in air in a concentration of nearly 1%, and therefore the term rare was challenged. In the last decade a few xenon and krypton compounds have been prepared under specic laboratory conditions, and the term inert has been challenged as well. In nature, however, their chemical nobility is well preserved, making them ideal tracers in hydrological systems. They have a number of advantages, including . . They are not involved in any chemical or biological activity. They enter groundwater from two distinct major sources: by equilibration with air during inltration or from deep-seated

Table 13.1 Noble Gases (ppm volume) in Dry Air at 1 atm (sea level) He 5.24 Ne 18.18 Ar 9340 Kr 1.14 Xe 0.086 287


Chapter 13

. .

origins, which include ushing of radiogenic products from aquifer rocks and from mantle-derived gases. The origin of these different sources is identiable by the isotopic composition. The initial concentrations of atmospheric noble gases in recharge water can be predicted from the ambient annual temperature and altitude of the suggested recharge area. The fact that there are ve noble gases provides valuable redundancy.

Let us begin the discussion with the atmospheric input.

13.2 Atmospheric Noble Gases and Their Dissolution in Water

The atmosphere is a well-mixed reservoir with known concentrations of noble gases (Table 13.1). These atmospheric noble gases have characteristic isotopic abundances that are given in Table 13.2. The solubility of the noble gases is given in Fig. 13.1, expressed in cc STP noble gas/cc water. STP stands for standard temperature (0 8C) and pressure (760 mmHg 1 atmosphere). What is the solubility of argon in distilled water at sea level at 15 8C? The answer, from Fig. 13.1, is 3.5 6 104 cc STP Ar/cc water. The lack of chemical interactions in the noble gases makes them ideal gases, and as such their solubility in water is directly proportional to their partial pressure in air. This, in turn, depends on the barometric pressure, which is linearly correlated to the altitude. The higher the altitude, the less noble gases dissolve in water. This relation is expressed in Fig. 13.2. The correction factor, read on the right vertical axis in Fig. 13.2, is multiplied by

Table 13.2 Isotopic Abundances of Atmospheric Noble Gases (chart of the nuclides, 1977) He Isotope 3 % 4 20 Ne 21 22 37 Ar 38 40

0.0014 100 Kr

90.51 0.277 9.22 Xe 84 86 128 1.91 129 130 131

0.337 0.063 99.60

Isotope %

80 2.25




134 10.4

136 8.9

11.6 11.5 57.0 17.3

26.4 4.1 21.2 26.9

The Noble Gases


Fig. 13.1 Solubility of atmospheric noble gases in fresh water at sea level (1 atm) as a function of the ambient temperature. (From Mazor, 1979b.)

Fig. 13.2 Atmospheric pressure variations as a function of altitude. (From the U.S. Standard Atmosphere, 1962.) Correction factors on the right axis serve to convert values at sea level (Fig. 13.1) to solubility values at desired altitude (dividing by the factor) or to normalize data at a given altitude to the corresponding value at 0 masl (multiplying by the factor). The last conversion is needed to read intake (recharge) temperatures from Fig. 13.1, which is for sea level (i.e., 760 mmHg) (Mazor, 1975).


Chapter 13

a solubility value observed at a given altitude in order to get the equivalent solubility (at the same ambient temperature) at sea level. Or the solubility at a given temperature at sea level (Fig. 13.1) can be divided by the correction factor in order to get the solubility at the same temperature at a selected altitude. The need for these procedures will be soon explained, but let us rst get familiar with them: What is the solubility of krypton at 18 8C on a mountain that is 2500 masl? The answer is worked out in steps: The solubility of krypton at 18 8C at sea level is (from Fig. 13.1) 7.5 6 108 cc STP/cc water. The correction factor for 2500 masl is (from Fig. 13.2) 1.35. The solubility of krypton at 18 8C and 2500 masl is 7:56108 5:56108 cc STP=cc water 1:35 The solubility of the noble gases depends on a third parameter: the concentration of dissolved ions in the water. The data in Fig. 13.1 are for salt-free water. Seawater, for example, dissolves 30% less. This effect has only seldom to be regarded in groundwater tracing, since recharge is in most cases relatively fresh.

13.3 Groundwater as a Closed System for Atmospheric Noble Gases

Recharge water equilibrates with air during its inltration and it dissolves atmospheric He, Ne, Ar, Kr, and Xe in amounts dened by the local altitude and the ambient temperature. Once water enters the saturated zone of groundwater, no further additions of atmospheric gases are possible since the rock pores contain only water. Release of dissolved gases in the saturated zone is not possible either, because of the hydrostatic pressure of the system. Because of these arguments it has been postulated that the nobles gases are kept in closed system conditions in groundwater, and therefore one can measure the noble gas concentrations in the water of a spring or well and calculate from them the ambient temperature at the recharge area (Mazor, 1972). A coastal spring was found to contain 12 6 109 cc STP Xe/cc water. What was the ambient temperature at the point of recharge (assuming the system remained closed)? From Fig. 13.1 it is seen that 12 6 109 cc STP Xe/cc water are dissolved in water that equilibrates with air at 12 8C. Hence, if recharge were at sea level, the ambient temperature would have been 12 8C.

The Noble Gases


A spring emerges at an altitude of 200 masl. The highest point in the potential recharge area is 400 masl, and the average altitude of the recharge area is (400 200)/2 300 m. In a water sample of this spring 10 6 109 cc STP Xe/cc water were found. What is the recharge temperature? Lets do the calculation in steps: 1. The altitude correction factor for 300 m is read from Fig. 13.2 to be 1.05. 2. Multiplying the observed xenon concentration by this factor, the equivalent concentration at sea level is obtained: 10 6 109 6 1.05 10.5 6 109 cc STP/cc water. Figure 13.1, reveals the equivalent temperature: 16 8C. In summary, it might be concluded that: . . The initial noble gas concentrations in recharged groundwater can be calculated from the ambient temperature and recharge altitude. The concentration of dissolved noble gases in groundwater (a spring or a well) can be used to calculate the ambient intake temperature, if the recharge altitude is known or assumed.

The scope of noble gas applications in groundwater studies is much greater than described thus far, but rst we have to check the basic assumption that groundwater provides closed system conditions for dissolved atmospheric noble gases.

13.4 Studies on Atmospheric Noble Gas Retention in Groundwater Systems: Cold Groundwater
Groundwater samples from various locations around the world have been analyzed for their noble gas isotopic composition and elemental concentrations. One such study was conducted by Herzberg and Mazor (1979) on four springs of simple hydrological structures (Fig. 13.3 and Table 13.3). The isotopic composition of the Ne, Ar, Kr, and Xe was found to equal that of air, revealing the atmospheric origin. The noble gas concentrations are given in Table 13.4. These data were multiplied by the respective altitude correction factors (Fig. 13.2) to obtain the noble gas concentrations normalized to 1 atm (sea level), as seen in Table 13.5. These values were then applied to calculate intake temperatures, which are given in Table 13.6 along with temperatures measured in the eld. Six points of temperature measurements seem to be especially informative along the hydrological cycle. These points are (Fig. 13.4):


Chapter 13

Fig. 13.3 Location of springs (circles) of simple hydrological systems in Israel selected for noble gas retention studies (Table 13.3).

T1the average ambient air temperature during the rainy season at the recharge location, obtained from meteorological surveys. T2the average annual air temperature at the recharge location, obtained from meteorological studies. T3the temperature at the base of the aerated zone, just above the water table. This temperature is deducible from the noble gas concentration. T4the highest temperature reached during the groundwater cycle, presumably obtained at the deepest point of circulation. T5the temperature observed at the spring or well head. T6the ambient air temperature at the site and time of sample collection. T4 is the only value we cannot measure, but if ow rates are high enough, T5 will be equal to or slightly lower than T4. T5, the spring or well temperature, may thus be regarded as a minimum value of T4. The data in Table 13.6 reveal the following observations: . Agreement between the intake temperatures calculated via Ar, Kr, and Xe is + 1 8C. This in itself indicates the systems are closed, since losses or gains would most probably be connected to fractionation that would introduce disagreements between the various calculated intake temperatures.

The Noble Gases

Table 13.3 General Data on Springs Selected for Noble Gas Retention Studies (Fig. 13.3) Altitude (m) of recharge area Sample no. OH-10 OH-13 H-6 14.9.74 20.5 300 225 150 2.10.74 3.3.75 22.0 22.0 520 270 20 Date Temperature (8C) maximum average minimum Description

Name of spring



Taninim 29














Issues on the fault of Mount Carmel on the contact with the Yzreal Plain A small spring in a basaltic region draining two adjacent hills One spring out of several issuing in the Kabara plain; seems to be recharged from the Shomron Mountains Issues on the eastern slopes of the Judean Mountains

Source: From Herzberg and Mazor (1979).



Table 13.4

Noble Gas Concentrationsa (cc STP/cc water) in Samples from Springs in Israel (Table 13.3)

No. Saadia Saadia Yavniel Taninim 29 Fara 2.10.74 4.3.75 14.9.74 19.3.75 22.7.74 22.0 22.0 20.5 23.5 20.5 17 12 21 18 23 20.7 + 1.0 20.4 + 0.4 21.3 + 0.9 21.3 + 0.3 18.8 + 0.4 (4) (4) (3) (3) (3) 3.00 + 0.10 2.99 + 0.08 3.01 + 0.06 2.98 + 0.04 2.72 + 0.11 (4) (4) (3) (3) (3)



Spring temperature (8C) Ne (6 108) Ar (6 104)

Ambient temperature (8C)

Kr(6 108) 6.49 + 0.24 6.40 + 0.25 6.33 + 0.33 6.31 + 0.09 5.83 + 0.11 (4) (4) (3) (3) (3)

Xe(6 109) 8.67 + 0.60 8.56 + 0.79 8.65 + 0.33 8.47 + 0.31 7.59 + 0.39 (4) (4) (3) (3) (3)

OH-10 OH-13 OH-6 OH-16 OH-5

Errors cited are mean errors for several samples collected at the same time (their number is given in parentheses). STP denotes 760 mmHg and 0 8C. Source: From Herzberg and Mazor (1979).

Chapter 13

The Noble Gases

Table 13.5 No. OH-10 OH-13 OH-6 OH-16 OH-5 225 450 550 1.024 1.049 1.068 Saadia Saadia Yavniel Taninim 24 Fara 270 1.030 21.3 21.0 21.8 22.3 20.1 Source Average recharge altitude (m) Ne (6 108) 3.09 3.08 3.08 3.13 2.90 Altitude correction factor Ar (6 104)

The Noble Gas Concentrations of Table 13.4 Normalized to 1 atm (sea level) (cc STP/cc water) Kr (6 108) 6.68 6.59 6.48 6.62 6.23 Xe (6 109) 8.93 8.82 8.86 8.89 8.11



Table 13.6 Intake (recharge) Temperatures Deduced from Noble Gasesa and Measured in the Fieldb (8C) Recharge area T1c average rainy season T2c average Ar 21 21 21 21 23 21 22 23 22 24 21 21 21 22 23 21 + 1 21 + 1 21 + 2 21 + 1 23 + 1 Kr Xe 19 19 21 19 16 Averaged 10 10 14 14 10 Noble gases, T3 Sampling site

No. Saadia Saadia Yavniel Taninim 19 Fara 2.10.74 4.3.74 14.9.74 19.3.75 22.7.74



T5 spring 22.0 22.0 20.5 23.5 20.5

T6 ambient air 17 12 21 23 23

OH-10 OH-13 OH-6 OH-16 OH-5

Applying the data of Table 13.5 and the solubility curves (Fig. 13.1). T1 T6 are dened in the text and in Fig. 13.4. c From various meteorological sources. d The cited errors were calculated from the errors of the individual runs as given in Table 13.4.

Chapter 13

The Noble Gases


Fig. 13.4 Denition of temperatures relevant to hydrological studies: T1 average temperature in the rainy season at recharge area; T2 average annual temperature at recharge area; T3 temperature at the base of the aerated zone, above the water table (deduced from the Ar, Kr, and Xe concentrations); T4 maximum temperature reached at the deepest point of the water path; T5 observed spring or well temperature at the time of sampling; T6 ambient air temperature at the time of sampling. (From Herzberg and Mazor, 1979.)

In the rst three cases (Saadia, Yavniel, and Taninim 29) the noble gas deduced temperatures (T3) are equal to, or 2 8C higher than, the average annual temperature. In contrast, they differ by about 10 8C from the average temperature of the cold rainy season. Hence, it seems that the temperature documented by the noble gases during equilibration with air at the base of the aerated zone equals the local average annual temperature. This makes sense because inltrating recharge water often descends at rates of a few meters per year or less. Hence, inltrating water is delayed in the aerated zone, adopting the average temperature prevailing underground. This topic will be further discussed in the next section. In the rst three samples of Table 13.6 the noble gas deduced temperature, T3, differs from the ambient air temperature at the time of sample collection, T6, revealing no equilibration at the point of emergence (in agreement with the previous paragraph). The last spring (Fara), however, shows T3 T6. This water issues below a slope of tallus, and equilibration of noble gases could take place prior to sample collection.

Good agreement, obtained for various cold groundwaters, between noble gas deduced intake temperature and average annual temperature at the recharge area prove the validity of the original assumption: groundwater is a closed system for the dissolved atmospheric noble gases.


Chapter 13

13.5 Further Checks on Atmospheric Noble Gas Retention: Warm Groundwater

The closed system conditions seen in cold groundwater systems may be further checked in warm springs, that is, in waters that are trapped at a depth of 12 km and get heated by local (normal) heat gradients. The rst study of this type was done on warm springs and wells (up to 60 8C) of the Jordan Rift Valley (Mazor, 1972). The isotopic compositions of the encountered dissolved Ne, Ar, Kr, and Xe were found to be atmospheric, that is, very close (in the range of the analytical accuracy) to the values given in Table 13.2. The atmospheric noble gases are presented in Fig. 13.5 in a ngerprint diagram. An overall similarity of the line patterns to those of air-saturated water at 1525 8C is clear. Thus the relative abundances of the four noble

Fig. 13.5 Noble gases dissolved in thermal waters in the Jordan Rift Valley. (Data from Mazor, 1972.) The nonsaline waters lie between the values of air-saturated water (ASW) at 15 and 25 8C, demonstrating the meteoric (atmospheric) origin and the closed-system conditions that prevailed in the ground. The saline Tiberias hot water is suggested to have originated by saline water entrapment, a hypothesis supported by the lower noble gas content (Mazor, 1972).

The Noble Gases


gases Ne, Ar, Kr, and Xe indicate they originated from air dissolved in the recharge water. The ngerprint lines in Fig. 13.5 are parallel to each other, but vary in their height on the concentration axis. What might be the explanation for this? The answer is differences in the recharge areas and, hence, in the initial noble gas concentrations due to differences in altitude (temperature and pressure). In one case, the Tiberias Hot Springs, the initial salinity played a signicant role. Lets have a closer look at the Tiberias Hot Springs case. It is lowest in Fig. 13.5, revealing the lowest noble gas concentrations. However, it has a salt concentration almost equal to seawater. So the initial noble gas concentration was as in seawater30% less than in fresh water under similar conditions. Hence, to normalize the Tiberias Hot Springs line in Fig. 13.5 and compare it with fresh water samples, the values have to be increased by 30%. In doing so, the Tiberias Hot Springs line falls right in the middle of the other Rift Valley warm waters, close to ASW 15 8C, agreeing with closed system conditions. The noble gases thus provide independent support of the origin of the Tiberias Hot Springs from saline water. As noble gas concentrations are obtained, the hydrochemist is always confronted with the need to establish whether the data reect the indigenous noble gas concentrations, or whether reequilibration with the atmosphere occurred prior to sampling. The problem is acute in springs: the samples are collected in the spring as deep as possible below the water surface, but did the water reequilibrate while owing below gravel, for example? Or did the water circulate in the springs outlet? An answer may be obtained by comparing the observed noble gas concentration with the concentration calculated for equilibration with air at the emergence temperature of the spring. Example: A spring emerges at 34 8C and is found to contain 3.8 6 104 cc STP Ar/cc water. Is it oversaturated, that is, does it contain more gas than expected from air equilibration at the emergence temperature? The airwater solubility at 34 8C is seen in Fig. 13.1 to be 2.5 6 104 cc STP Ar/cc water. Hence, the observed value of 3.8 6 104 cc STP Ar/cc water is oversaturated by 3:86104 6100 152% 2:56104 of the equilibration value at the temperature of emergence. (The observed value of Ar concentration indicates a recharge temperature of 10 8C. Is this right?) The observed krypton and xenon concentrations in each water source in the Rift Valley study were converted in this way to percent air saturation


Chapter 13

in Fig. 13.6. It is seen that the samples contain more than 100% air saturationthey are oversaturated, indicating reequilibration subsequent to heating did not occur. This diagram shows the importance of duplicate or triplicate sampling. The one low value of sample 3 is clearly wrong due to gas loss during sampling, the higher sample 3 values being more representative (and not the average). Warm springs are a rigorous check of closed-system conditions for the atmospheric noble gases, as their waters circulate deep and their ages are relatively high. Figures 13.7 and 13.8 show results for another case, in Swaziland.

Fig. 13.6 Percentage of air saturation of krypton and xenon for the Jordan Rift Valley waters. The values were obtained by dividing the measured amounts by those expected for water equilibrated with air at the temperature at which each sample was collected. All samples, except one, were found to be air supersaturated, indicating that the rare gases were retained under closed system conditions. Differences in duplicate samples are attributed to gas losses to the atmosphere prior to sampling (Mazor, 1975).

The Noble Gases


Fig. 13.7 Noble gas pattern of atmospheric noble gases in warm springs in Swaziland. The isotopic compositions were found to be atmospheric, and the abundance patterns, similar to ASW 25 8C, conrm this. The variations in concentrations are caused by different recharge altitudes (Mazor et al., 1974).

Fig. 13.8 Percent air saturation of krypton and xenon for warm springs in Swaziland (same spring numbers as in Fig. 13.7). All samples were oversaturated at the temperature of emergence (3552 8C), indicating the systems were closed (Mazor et al., 1974).


Chapter 13

13.6 Identication of the Nature of the Unsaturated Recharge Zone: A Porous Medium or a Karstic System
In Table 13.7, data for two karstic springs from northern Israel and one from eastern Switzerland are given. The table includes 1. Ne, Ar, Kr, and Xe concentrations. 2. The noble gas concentration in air-saturated water at the respective recharge temperatures and altitudes. 3. Division of (1) by (2), multiplied by 100 provides the percent concentration relative to the expected air-saturated water at the recharge location. The values (Fig. 13.9) are signicantly different from what we have seen so far: Neon concentrations are 144172%. Thus excess atmospheric neon (recognized as atmospheric by its isotopic composition) is present. The other noble gases are also present in concentrations exceeding 100%, but the excess decreases towards xenon. In other words, the retention percentage pattern is Ne > Ar > Kr > Xe.

Table 13.7 Stages in the Calculation of Percentage Noble Gas Retention in Karstic Water Samples Data Measured values 10 STP/cc watera

Karstic spring cc


Ar 36700 33800 39600 28000 32000

Kr 7.85 6.97 8.81 6.70 7.00

Xe 1.02 0.97 1.13 0.96 1.09 106 101 104

ASW, 14 8C, 1700 mb ASW, 10 8C, 1000 m % retention, relative to AWS at recharge pointc
a b

Dan, Israel 28.8 Banias, Israel 24.1 Source de la Doux, 28.6 Switzerland recharge of Dan and 16.7 Banias springs recharge of Source de 18.3 la Doux Dan 172 Banias 144 Source de la Doux 156

131 116 121 104 124 116

Data from Herzberg and Mazor (1979). The values, in 10 8 cc STP/cc water, were calculated from the relevant solubility values divided by the corresponding altitude correction factor. c (a/b) 6 100.

The Noble Gases


Fig. 13.9 Percent air saturation for karstic springs (Table 13.7). Values are above 100% and the lines reveal a reversed pattern of Ne > Ar > Kr > Xe.

The explanation is that free air has been siphoned into the karstic water, in addition to the initial dissolved air. The solubility of the noble gases is smallest for helium and increases toward xenon. This should not be confused with Fig. 13.1, which was obtained by taking the solubility of each noble gas and multiplying it by its abundance in air (Table 13.1). (One can obtain the noble gas solubility for a selected temperature by dividing the respective values in Fig. 13.1 by the abundance values of Table 13.1). Free air is relatively richer in the less soluble gases, therefore its addition to already saturated water in the karstic springs causes (1) excesses over 100% saturation and (2) the excess pattern of Ne > Ar > Kr > Xe. The excess atmospheric air was observed to be negatively correlated to spring discharges, reecting that larger parts of the system contain air in the low ow season, and when the water ows through narrowing conduits the air is sucked in. In the high ow season most of a karstic system is lled with water and less air can be siphoned (Herzberg and Mazor, 1979). Excess air in groundwater has been reported by Heaton and Vogel (1981) for cases of special soil conditions observed in South Africa. Hence, periodic noble gas measurements are desired: a negative correlation with discharge will establish the karstic nature of a studied spring or well.

13.7 Depth of Circulation and Location of the Recharge Zone

Inltrating water is, in many cases, delayed in the aerated zone long enough to equilibrate to the ambient temperature. In shallow depthsless than 10


Chapter 13

15 mthis equilibrated temperature will be close to the local average annual temperature. Daily temperature uctuations are damped in less than 0.5 m (Fig. 13.10), and seasonal uctuations are damped in a few meters. If the temperature of a spring or well is higher than the noble gas deduced temperature (T5 > T3 in Fig. 13.4), then the additional temperature reects heating by the local geothermal gradient. If this gradient is known, then dividing the temperature gain by the gradient will provide the depth to which the water is circulated in the saturated zone. Example: The water of the Taninim spring is seen in Table 13.6 to emerge at 23.5 8C, whereas the noble gas deduced temperature at the base of the aerated zone is 21 + 1 8C. How can this difference be explained? The additional 2.5 8C resulted from equilibration of the aquifer temperature. The local heat gradient is not known, so let us use the common value of 3 8C/ 100 m. Accordingly, the water circulated to a depth of 80 m or more in the saturated zone. (It might be more because partial cooling during ascent could occur).

Fig. 13.10 Daily temperatures in soil proles measured in 1970 at the Santa Rita Experimental Range, Tucson, Arizona. The daily uctuations are seen to be damped at 30 cm. (After Foster and Fogel, 1973.)

The Noble Gases


Locating recharge areas. A well in a coastal plain provides fresh water at 26 8C. The question came up of whether it is recharged by local rain or snowmelt on the 20-km distant mountains. To resolve this problem the noble gases were measured and the following concentrations were found: 2.1 6 107 cc STP Ne/cc water and 3.0 6 104 cc STP Ar/cc water. The local heat gradient has been established to be 2.5 8C/100 m. Where is the recharge location? The neon curve in Fig. 13.1 is seen to vary little with temperature, and therefore it is of little use to the calculation of the intake temperature. The argon curve is, in contrast, sensitive to temperature changes. An intake (base of aerated zone) temperature of 19 8C is obtained. Hence, 26 8C 19 8C 7 8C is the temperature gain obtained by the depth of circulation. Applying the local heat gradient, the depth of circulation is 7 6 100/2.5 280 m. The depth of circulation indicates remote recharge at a relatively high altitude. If so, a respective altitude correction should be applied to the raw noble gas data, resulting in an intake temperature lower than 19 8C, further supporting mountain recharge. This example demonstrates the potential use of the atmospheric noble gases in identifying a recharge location. Combined with stable isotope measurements of hydrogen and oxygen in water, that is, dD and d18O, a data matching is obtained. One can calculate the recharge altitude from the dD and d18O values (section 9.8) and then, applying the respective altitude correction, one can calculate the intake temperature, thus checking the validity of the suggested recharge location. Furthermore; the difference between observed emergence temperature and noble gas deduced intake temperature will give the minimum depth of circulation and thus tell whether the water moves underground in a shallow path or a deep path.

13.8 Paleotemperatures 13.8.1 Principles and Importance

Old groundwaters contain dissolved noble gases in concentrations that were dened by the ambient temperature that prevailed at the time of recharge. Coupling of groundwater dating methods, for example, 14C dating, with intake temperatures calculated from observed Ar, Kr, and Xe concentrations (section 13.3) may provide relevant paleotemperatures (Mazor, 1972). This noble gas based method is the only method that can be used to directly reconstruct paleotemperatures. Other techniques of paleoclimatic reconstruction are more general, combining humidity and temperature in relative terms. Other methods are based on the width of tree rings, the types of pollen in dated paleosoils, the composition of stable hydrogen and oxygen


Chapter 13

isotopes in dated groundwaters, or variations in the distribution of ancient human settlements. The application of noble gas based paleotemperature determination is demonstrated in the following sections by case studies, and thereafter some aspects of paleoclimatic feedback are discussed as a requirement of a better understanding of the reconstructed paleotemperatures. Finally, the relevance of paleotemperatures to the topic of global temperature changes is addressed.

13.8.2 Case Studies

An example of a noble gas paleotemperature study was conducted by Andrews and Lee (1979) in the Bunter sandstone aquifer in eastern England. The noble gases were studied as part of an intensive hydrochemical study, discussed in section 11.9. Table 13.8 contains the noble gas concentrations in three sections of the studied groundwater system: group Arecharge zone, unconned system; group Ban adjacent conned system; group C another conned system (section 11.9). The observed noble gas concentrations were used to calculate intake temperatures. The paleotemperatures are plotted versus emergence temperatures (indicating depth) in Fig. 13.11. The results: 10 + 1 8C for the shallow group A; 9 + 1 8C for the medium depth group B; and 4 + 1 8C for the deepest group C. Other examples of noble gas paleotemperatures have been reported by Rudolph et al. (1983). They calculated temperatures as low as 12 8C 22,000 years ago (dated by 14C) in Germany, accompanied by relatively negative dD and d18O values and a measurable excess of radiogenic helium.

13.8.3 Paleotemperatures During the Last Glacial Maximum: Real or Apparent Differences Between Terrestrial and Oceanic Evidence
The last glacial maximum occurred about 18,000 years ago, well within the dating range of 14C. The event was quite dramatic, and eld evidence reveals that the snow lines of the higher mountains were up to 1000 m lower than their present positions. In connection with speculations connected with possible man-induced global climatic changes in the future, it is of much interest to establish how many degrees lower the temperature was during the last glacial maximum. Fauna abundances and 18O studies of dated oceanic sediment cores revealed that the low-latitude ocean surface water was colder by less than 2 8C (Broecker, 1986). In contrast, noble gas paleotemperatures dened in groundwaters from the Carizzo aquifer (Texas) revealed that during the last glacial

The Noble Gases


maximum the temperature was 5.2 + 0.7 8C lower than the local present temperature (Stute et al., 1995a). A comprehensive study of noble gases dissolved in groundwater conducted in the San Juan basin, New Mexico, revealed that the temperature was 5.5 + 0.7 8C lower than the local present temperature (Stute et al., 1995b). A similar study in tropical Brazil revealed a drop of 5.4 + 0.6 8C during the last glacial maximum (Stute et al., 1995b). The meaning of the presented paleotemperatures during the last glacial maximum warrants some discussion. For the global change issue of interest are multiyear average temperatures that prevailed in different places all over the Earth. However, there seems to exist a paleohydrological effect that is of importance: even a slight drop in the average temperature seems to cause signicant lowering of the snow line, which increases the signicance of snowmelt in the local recharge. Snowmelt recharge is, in turn, coupled with increasing importance of karstic recharge, on account of porous medium recharge. Thus the recharge water entered the saturated zone at relatively low temperatures, that are somewhat between the snowmelt temperature and the multiyear average ambient temperature. In other words, the cooling of the last glacial maximum yielded an increased temperature drop in the studied paleowatersreecting a seasonal paleotemperatureand the average annual temperature was somewhat higher. Broecker (1986) and Stute et al. (1995a) pointed out that there seems to be a disagreement between the paleotemperature deduced for the last glacial maximum based on oceanographic sediments (less than 2 8C) and the signicantly larger temperature drop (5.2 8C) deduced from noble gases in dated groundwaters. The discussed accentuation of the noble gas paleotemperature record, as a result of increasing importance of recharge by snowmelt, may reconcile the oceanic and continental paleotemperature records related to the last glacial maximum: the marine record may reect the multiyear average ambient temperature, whereas the studied paleowaters may reect temperatures closer to the snowmelt recharge. This hypothesis can be checked by measuring noble gases in groundwaters for locations that were remote of any paleo-snow line and had porous medium recharge.

13.8.4 The Relevance of Paleotemperatures to the Question of Possible Manmade Global Climatic Changes
Recently much research has been devoted to the possible climatic consequences of man-induced changes in atmospheric compounds and landscape features. Examples are increases in the concentration of CO2 and other greenhouse gases and dust or the thickness of the ozone layer, as well as large-scale deforestation and desertication. Opinions vary as to the

308 Deduced intake temperature (8C) Ne 0.8 0.5 2.6 0.5 0.6 1.5 1.7 2.9 0.3 0.2 1.4 0.5 0.6 0.2 4.0 4.3 7.4 4.3 4.2 6.2 6.5 7.8 5.1 4.9 3.5 4.3 4.2 4.6 2.09 2.09 2.09 2.09 2.09 2.01 2.07 2.12 2.09 2.02 2.09 2.07 2.05 2.08 4.02 4.02 3.87 4.05 3.83 4.07 3.94 4.16 4.09 3.89 4.04 3.76 4.28 3.89 8.65 8.68 8.69 8.78 9.02 8.71 9.14 9.12 8.70 8.74 8.64 8.84 9.13 8.80 10 10 10 10 10 15 11 9 10 (15) 8 11 10 10 Ar 9 9 10 9 11 8 9 7 8 10 7 11 11 10 Kr 12 12 12 12 11 12 11 11 12 11 12 11 11 12 Average 10 + 1 10 + 1 11 + 1 10 + 1 11 + 1 12 + 2 10 + 1 9+2 10 + 2 11 + 1 9+2 11 + 1 11 + 1 11 + 1

Table 13.8 Noble Gases (cc STP/cc water) of Groundwaters in the Triassic Sandstone Aquifer in Eastern England Deduced Intake Temperatures (read from solubility curves, Fig. 13.1), and Radiogenic Hea

Group No. 5 9 12 6 1 3 10 8 4 7 11 13 14 15 Elkesley, No.6 Elkesley, No.5 Elkesley, Clarks No.1 Far Baulker, No.3 Amen Corner, No.1 Boughton, No.2 Retford, Clarks No.2 Ompton, No.2 Franseld Rufford, No.3 Retford, Orsdall No. 1 Everton, No.1 Everton, No.3 Retford, Whisker Hill


He Ne Ar Kr Rad. Hea 8 7 4 8 (6 10 ) (6 10 ) (6 10 ) (6 10 ) (10 8)


Chapter 13

The Noble Gases


16 17 21 20 19 26 24 25 30 28 31 22 32

Halam, No.1 Markham Clinton, No.1 Egmanton, B.P. Caunton Retford, Grove No. 2 Gainsborough, B.P. Newark, British Gypsum Newark, Castle Brewery Gainsborough, Humble Carr Newton, No.2 Gainsborough, No.3 Rampton South Scarle

14.1 4.3 10.8 3.6 8.4 23.7 21.9 25.9 27.2 17.3 34.3 19.3 17.6

2.23 2.09 2.11 1.84 2.14 2.20 2.29 2.27 2.18 2.27 2.20 2.27 2.20

4.15 3.99 4.07 3.65 4.19 4.58 4.86 4.78 4.49 4.72 4.52 4.68 4.51

8.82 8.74 9.13 7.93 9.13 9.85 10.63 10.50 10.10 10.54 10.28 10.48 9.96

9.2 0.5 5.9 1.1 3.6 18.7 16.9 20.9 22.2 12.3 29.3 14.3 12.6

6 10 9 (25) 5 5 3 4 5 4 5 4 5

7 9 8 12 7 3 2 2 4 3 4 3 4

12 12 11 15 11 8 5 5 7 5 6 5 8

8+2 10 + 1 9+1 9+ 8+2 5+2 3+1 4+1 5+1 4+1 5+1 4+1 6+2

a Observed He minus atmospheric He, read from the solubility curve (Fig. 13.1), applying the average deduced intake temperature (last column of present table). Source: From Andrews and Lee (1979).



Chapter 13

Fig. 13.11 Noble gas deduced intake temperatures versus observed emergence temperatures (Table 13.8) in wells of the Bunter sandstone aquifer in eastern England. The dashed line is an equal temperature line, that is, noble gas temperature equals observed temperature. Group A data are around this line; group B reveals slightly colder paleotemperatures (810 8C); and group C reveals signicantly colder values (35 8C).

expected climatic changes, and a knowledge of the natural uctuations is of great relevance: will the man-induced changes be in the range of the natural uctuations or higher? This, in turn, will tell researchers to what degree manmade global temperature changes can be read from temperature records. For this reason, as many continuous paleotemperature records as possible are needed, of as long a duration as possible (mainly limited by the available dating methods).

13.9 Sample Collection for Noble Gas Measurements

Noble gases are measured with special mass spectrometers. The size of the water samples needed is 510 cc. The major difculty in noble gas work is the absolute need to avoid air contamination: a bubble of air present in the collected sample may contain more noble gases than the entire sample. Two techniques are in use to sample for noble gases: (1) lling water in glass tubes with special glass stopcocks, and (2) lling copper tubes, closed at their ends with special clamps. The sampling method should be talked over with the laboratory staff, who should provide the collection vessels and detailed sampling procedures. Since sample collecting has to be done with

The Noble Gases


care, it is recommended that laboratory personnel join the eld team to do the sample collections, if possible. The number of laboratories that measure noble gases in water samples is slowly but steadily increasing. The know-how is actually available in most laboratories that do potassium argon dating of rocks. Because of increased demand from eld hydrochemists, more laboratories are willing to enter the domain of noble gas hydrology. Eventually, noble gas measurements will become as routine as dD, d18O, tritium, or 14C measurements.

13.10 Summary Exercises

Exercise 13.1: Fill in the missing data of air solubility, at sea level (in cc STP/ cc water):
Temperature 158C 22 8C 51 8C He Ne Ar 3.5610



Exercise 13.2: What is the solubility of the ve noble gases at 5 8C and 1500 masl? Exercise 13.3: Calculate the intake (recharge) temperature for (a) a well with 3:26104 cc STP Ar/cc, located at 250 masl, with the highest point in the recharge area at 650 masl; (b) a spring with 106108 cc STP Kr/cc water, emerging at 1000 masl, the highest point of recharge being 1300 masl; and (c) an artesian well with 126109 cc STP Xe/cc water, with an average recharge intake altitude of 850 m. Exercise 13.4: A coastal spring emerges at 32 8C and contains 3:76104 cc STP Ar/cc water. What is the minimum depth of circulation of the water in the saturated zone? Exercise 13.5: A spring issues in a plain, the temperature being 24 8C, and its water was found to contain 2:16107 cc STP Ne/cc water, and 3:86104 cc STP Ar/cc water. What is the intake temperature, and what is the depth of water circulation? Is the recharge location nearby in the plain or distant in the mountains?


14.1 Sources of Radiogenic 4He Dissolved in Groundwater

The radioactive decay of uranium and thorium results in the formation of a series of isotopes that are radiogenic by themselves and keep disintegrating into stable lead isotopes. These radioactive disintegrations are accompanied by the emissions of 4He atoms. Three such radioactive series exist:
238 235 232

U?206 Pb 8 4 He U?207 Pb 7 4 He Th?208 Pb 6 4 He

The production rate of the radiogenic helium in each of these decay series is determined by the respective half-lives, and the overall helium production per unit rock is determined by the concentration of uranium and thorium in the rock (common rocks containing uranium and thorium in parts per million (ppm) concentrations). The radiogenic helium is partially released from the crystal lattices of rocks and is dissolved in water that is in contact with the rocks. The production of helium is constant in any given set of rocks, and the amount dissolved in stored groundwater is proportional to the duration of water storage. This point is demonstrated by the comparison of groundwater ages deduced from 14C and helium concentrations observed in three groups of groundwater of the Bunter sandstone in eastern England (Fig. 11.26). A linear correlation is observed, supporting the 14C-deduced ages and

Helium-4 and Argon-40 Dating


demonstrating the applicability of radiogenic helium as an age indicator. The term age indicator is used in regard to radiogenic helium to emphasize the semiquantitative, yet hydrologically valuable, nature of the helium dating method. The 14C dating method is based on a known concentration of 14C in the initial water and depletion of 14C with age. Thus, the older the water gets, the more difcult it is to measure the 14C that is left in it. The 4He method is just the opposite: the initial concentration of radiogenic helium is zero in newly recharged groundwater, but it accumulates with age, and the older the water is, the easier it is to measure the concentration of the radiogenic 4He. Thus, the two dating methods are complementary. A practical limit of 14C dating of groundwater is about 25,000 years, whereas for radiogenic 4He the dating range is 104108 years.

14.2 Parameters Determining Helium Concentration in Groundwater

Originally, researchers (Andrews and Lee, 1979; Marine, 1979) assumed that radiogenic helium formed in rocks is dissolved in the associated water. Accordingly, the amount of radiogenic helium accumulating in groundwater is proportional to the time in underground storage, the emanation efciency of helium from the rocks (nearly 1 in aged rocks), the concentration of uranium and thorium in the hosting rocks, and the rock:water ratio. The amount of helium accumulating in groundwater (expressed in cc STP/cc water) is thus determined by the following equation (Bosch, 1990): He 107 t xHe 1:21U 0:287Th d rock:water where U and Th are the concentration of uranium and thorium in the host rocks, here expressed in g/g (the respective coefcients incorporate the halflives and number of helium atoms formed along each disintigration chain (Zartman et al., 1961). The rock:water ratio in common rocks ranges between 4 and 20, and is calculable from the effective porosity. xHe is the emanation efciency of helium from the rocks (nearly 1); t is the storage time, or age, of the water, in years; and d is the rock density. Example: The yearly accumulation of radiogenic helium in a typical groundwater can be calculated applying xHe 1, U 3 ppm, and Th 12 ppm (as in the average crust), d 2.5 g/cc, and a rock:water ratio of 4. The helium accumulation for 1 year is He 107 111:2136106 0:287126106 2:54 7:1012 cc STP=cc water


Chapter 14

The equation of the accumulation of radiogenic helium in groundwater is based on a number of assumptions: . . . . . . . All the emanated helium is dissolved in the associated water. No oversaturation occurs, and therefore no helium is lost. No helium is added by diffusion from rocks outside the aquifer. Mantle-derived helium is negligible, or may be subtracted, applying 3He:4He ratios. No mixing of groundwaters of different ages takes place. No helium (or other gases) was lost or gained by phase seperation underground. No helium (or other gases) was lost during ascent to the sample collection point.

These assumptions are discussed in the following sections. Examples of helium concentrations in groundwaters of the world are given in Table 14.1.

14.3 Case Studies and Observed Trends in the Distribution of Helium Concentrations in Groundwater Systems
Helium-rich groundwaters are as a rule encountered only in conned systems situated deep below sea level, an observation that in itself indicates that one is dealing with stagnant systems (section 2.13). Examples, included in Table 14.1 (from Mazor and Bosch, 1992a), are . . . . . . . The Bunter sandstone aquifer, England, reaching a depth of up to 400 m (Andrews et al., 1984) The Molasse Basin, Austria, in which Oligocene, Cretaceous, and Jurassic aquifers reach depths from sea level to 2000 m (Andrews et al., 1985, 1987) The Paris Basin, in which Jurassic aquifers are encountered at depths of 16001850 m (Marty et al., 1988) The Great Hungarian Plain, in which Plio-Miocene aquifers reach a depth of 1000 m (Deak et al., 1987) The Savannah River Plant site, United States, in which a conned Cretaceous aquifer reaches a depth of 300 m (Marine, 1979) Uitenhage, South Africa, where a quartzite aquifer attains a depth of 70470 m below the surface and up to 222 m below sea level (Heaton, 1984) The Great Artesian Basin, Australia, in which a Jurassic aquifer is up to 2000 m deep (Habermehl, 1980)

Helium-4 and Argon-40 Dating Table 14.1 4He Concentrations in Groundwaters Around the World (108 cc STP/cc water)
Sample Retford, U.K. Gainsborough, U.K. Blumau 11, Austria Blumau 32, Austria Uitenhage 14, South Africa Uitenhage 11, South Africa Uitenhage 22, South Africa Stampriet 45, South Africa Stampriet 6, South Africa Stampriet 50, South Africa Stripa, Sweden Stripa, Sweden Lincolnshire, U.K. Molasse, Austria: Ried 3 Aurolzmunster Schallerbach 2 Geinberg Bottstein, Switzerland Great Hungarian Plain: Heves Heves Kaba Savannah River Project, U.S. Paris Basin Great Artesian Basin: The Gap Tiberias, Israel Zin 5, Israel Hammat Gader, Israel Die Bad, S.A. Lilani, S.A. Natal Spa, S.A. He 3.6 29.3 61.7 1152 2 425 3970 115 6630 9330 Remarks Triassic, sandstone Triassic, sandstone Tertiary, sedimentary Ord., quarzite Ord., quarzite Ord., quarzite Sandstone Sandstone Sandstone References


39,000 345 m, granite 182,000 820 m, granite 1400 Jurassic, limestone 14 330 1900 5900 21,000 22 164 1000 20,000 90,000 13,000 2700 7 980 21 3500 14,100 Miocene, various sedimentary Miocene, various sedimentary Oligocene, various sedimentary Jurassic, limestone 621 m, granite 370 m, Pliocene, sedimentary 720 m Pliocene, sedimentary Quaternary, sedimentary Cretaceous, sedimentary Jurassic, limestone Jurassic, sandstone Rift Valley fault Rirt Valley ll Rift Valley system Fault, Cape System sedimentary Archaean metamorphic Archaean metamorphic

Andrews and Lee (1979) Andrews and Lee (1979) Andrews et al. (1984) Andrews et al. (1984) Heaton (1984), Talma et al. (1984) Heaton (1984), Talma et al. (1984) Heaton (1984), Talma et al. (1984) Heaton (1984), Talma et al. (1984) Heaton (1984), Talma et al. (1984) Heaton (1984), Talma et al. (1984) Andrews et al. (1982) Andrews et al. (1982) Andrews and Lee (1980) Andrews et al. (1985) Andrews et al. (1985) Andrews et al. (1985) Andrews et al. (1985) Andrews et al. (1985) Balderer (1985) Deak et al. (1987) Deak et al. (1987) Deak et al. (1987) Marine (1979) Marty et al. (1988) Marty et al. (1988) Mazor (1972) Mazor (1972) Mazor et al. (1973a) Mazor et al. (1983) Mazor et al. (1983) Mazor et al. (1983)


Chapter 14

14.4 Mantle Helium

The concentration of helium in air-saturated water is at most 5 6 108 cc STP/cc water, as seen in Fig. 13.1. Any excess above this concentration is of nonatmospheric origin. In terrains located on stable parts of the crustal plates, radiogenic helium is the sole nonatmospheric source. However, along plate margins and in volcanic systems, mantle helium is added to groundwater as well. These mantle helium contributions are noticeable by their relatively high 3He:4He ratios and rarely reach 50% of the observed helium. In addition, mantle helium is mainly added by release from mantleproduced rocks. This release is in itself time correlated and interferes only slightly, if at all, with the application of helium as an age indicator.

14.5 The Helium-Based Groundwater Age Equation

During migration and subsurface storage groundwater comes into contact with crustal rocks that continuously release helium from the decay of uranium and thorium. The basic assumption is made that the water acts as a sink for the helium evolved from the local rocks. The age of groundwater, t, is calculable from the equation given in section 14.2. Example: In the Milo Holdings 3 well, 1421 m deep, in the Jurassic rock sequence of the Great Artesian Basic, east Australia, the helium concentration of 1000 6 108 cc/cc water was found (Mazor and Bosch, 1990). The following local parametric values were applied to calculate the water age: xH 1; U 1.7 ppm; Th 6.1 ppm; d 2.6; effective porosity of 0.2 or a rock:water ratio of 4. Thus the age of this groundwater was found to be t 10006108 =f107 11:211:76106 0:2876:16106 2:64g 2:56106 years The obtained age for the deep water in the artesian Milo Holdings 3 well is semiquantitative because of uncertainties in the parameters applied in the calculation. Yet the order of magnitudemillions of yearsis of utmost importance: the water resource is not renewed, but it is entirely shielded from the surface and, hence, is immune to anthropogenic pollution. The low helium concentrations of rocks of known ages indicate emanation efciencies of 0.81 (Podosek et al., 1980; Zaikowski et al., 1987). The concentrations of uranium and thorium vary by a factor of 10 in common rocks, but knowledge of the lithologies of the main aquifer rocks can narrow the uncertainty to a factor of three or less. The rock:water ratio is more difcult to assess, but reasonable values are 420. Local information

Helium-4 and Argon-40 Dating


from drilling cores and logs and hydrological considerations may reduce the estimate error of this parameter to a factor of less than three. Thus uncertainties in the parameters of the age equation introduce errors of at most one order of magnitude to the helium-based groundwater age calculation. Helium can be reliably measured in waters with an age of 104 years, but the age of groundwaters varies widely and may reach 108 years. Thus the measurable helium concentrations in groundwater may vary over four orders of magnitude due to differing ages; therefore, helium concentration data are the most variable parameter of the age equation. In summary, the various parameters of the helium-based age equation can be resonably well estimated for each case study, and the water age can be calculated semiquantitatively. Thus the available methods cover the whole range of groundwater occurrences, with some overlaps: decades (tritium dating), 102103 years (14C dating), 105106 years (36Cl method), 104108 (4He dating), and 105108 (40Ar dating, still in development).

14.6 Comparison of Helium-Based Water Ages and Hydraulically Calculated Ages

Helium ages in conned groundwater systems are frequently greater than the corresponding hydraulic ages (section 2.10). Some examples include . Andrews et al. (1984) calculated ow velocities of 0.74 m/year for the conned Bunter sandstone groundwater system in eastern England. Hence, along the 20-km down-gradient ow in the study area the water should attain a hydraulic age of up to 80,000 years, whereas the corresponding helium age is 300,000 years. At Blumau, Austria, Andrews et al. (1984, 1985) calculated a hydraulic age of 7007000 years but obtained a helium age of 400,000 years for well 32 in the Molasse Basin; and the Birnbach well, in the deep Jurassic aquifer, yielded a helium age of * 10 million years. Heaton (1984), discussing the conned groundwater systems of Uitenhage and Stampriet, South Africa, concluded that the helium ages are 70 times greater than the hydraulic ages. Torgersen and Clarke (1985) found for the conned Jurassic aquifer in the Great Artesian Basin, Australia, that the observed helium concentrations were 70 times higher than expected for their calculation of the hydraulic ages.

. .


Chapter 14

Discrepancies of this type led the above-mentioned investigators to the conclusion that helium-based water ages are exaggerated. It was thus suggested by these researchers that the assumption that all the formed helium is dissolved in the rock-associated groundwater is wrong, and that the measured waters harvested helium that diffused from a thick sequence of the crust. This crustal helium diffusion model is ruled out by observations discussed in the following two sections (14.7 and 14.8). The helium-based groundwater dates seem to be valid, as can be checked by means discussed in sections 14.11 and 14.12. In contrast, it has been suggested that the hydraulic calculations of groundwater age have their shortcomings, often producing too young groundwater ages (Mazor and Nativ, 1992, 1994). The hydraulic travel time or age calculation applies Darcys law (section 2.10), which assumes hydraulic interconnection between wells from which data are applied. Failure to identify hydraulic barriers that separate different groundwater systems will result in apparent too young ages to be calculated.

14.7 Does Helium Diffuse Through the Upper Crust?

Water has a high helium dissolution capacity, and groundwaters in nature contain helium in a concentration range spanning over ve orders of magnitude, as seen in Table 14.1. In all these cases the partial helium pressure in the aquifers was orders of magnitude below the hydrostatic pressure, not to mention the lithostatic pressure, ensuring no gas losses took place. The water in each aquifer dissolves all the available helium and shields the overlying aquifers from helium uxes of the type suggested by the crustal helium diffusion model.

14.8 Helium Concentration Increases with Depth: Groundwater Acts as a Sink of Helium
In conned groundwater systems deeper water strata often contain higher helium concentrations. This pattern is observed with depth increase along the dip of conned aquifers or in samples obtained from a sequence of aquifers of different depths sampled at one location. In some examples, presented in Fig. 14.1, the depth of the water is known from direct measurements, and in others it is reected in the temperature, which increases with depth. The increase in helium concentration with depth is taken as an indication that the deeper waters are older, that is, they have been stored for longer times as compared to shallower waters. In this context it should be

Helium-4 and Argon-40 Dating


Fig. 14.1 Helium concentrations as a function of aquifer depth or temperature (following Mazor and Bosch, 1992a); Bunter sandstone aquifer, eastern England (data from Andrews et al., 1984); Stripa granite, Sweden (data from Andrews et al., 1982); Blumau, Austria (data from Andrews et al., 1984); Molasse Basin, Austria (data from Andrews et al., 1981); Great Artesian Basin, Australia (data from Torgersen and Clarke, 1985).


Chapter 14

remembered that the cited groundwater systems are conned below sea level and are devoid of drainage or have restricted drainage (along major faults or due to abstraction). The water in such deep basins may have been stored there since the burial of the conning rocks or since subsidence of these rocks to below the depth of the former base of drainage. In certain cases one may deal with genuine connate water, stored in the rock voids since their formation. The increase in helium concentration with depth is in many cases distinct, as seen in Table 14.1 for the examples of Blumau, Uitenhage, Stampriet, the Molasse Basin, the Great Hungarian Plain, and the Great Artesian Basin. The increase of helium concentration with depth in these examples cannot be explained by helium diffusion from deep parts of the crust. This would require unrealistic high diffusion gradients. As the examples of Table 14.1 reveal, helium increases by factors of 220 over depth increases of only a few hundred meters. The existence of neighboring groundwater units, or compartments, with different helium concentrations indicates a high degree of helium xation and a negligible degree of diffusion. Thus helium dissolution in water seems to be the major mechanism of this xation, as will be discussed later.

14.9 Effect of Mixing of Groundwaters of Different Ages on the Observed Helium Concentration
As discussed in sections 6.6, 6.7.4, 6.11.4, 10.6, and 11.10, mixing of groundwaters before emergence at the surface occurs naturally or as a result of abstraction operations and is rather common (Mazor, 1985, 1986; Mazor et al., 1973a). The helium concentration in a groundwater mixture has no meaning in terms of age. Hence, a check for possible mixing of waters should be performed before helium concentration is applied for groundwater dating. This can be done with chemical, physical, and isotopic data obtained from a number of hydraulically relevant water sources or observed in periodically collected samples of springs or wells (Mazor et al., 1985). Mixing can also be established by discordant groundwater ages (Mazor, 1986). Examples of discordant ages, obtained by applying tritium, 39Ar, 14C, and He data, are given in Table 14.2 for wells in the East Midlands Triassic aquifer in England. Thus it is highly recommended that water measured for helium also be measured for other age indicators. Samples with distinct tritium concentrations but low 14C concentrations represent mixtures. Similarly, 14C ages that are lower than the corresponding helium ages indicate that one deals with a mixture. The age pattern of mixed waters is intrinsically tritium age < 39Ar age < 14C age < 4He age.

Helium-4 and Argon-40 Dating


Observation of discordant ages provides information that is crucial to the understanding of a studied groundwater system. Information on the age of the intermixing water end members may be obtained from their reconstructed parameters (Mazor et al., 1986). In summary, the age of the young end member is less than the lowest age obtained, and the age of the oldest end member is higher than the highest age calculated by applying the raw data.

14.10 Helium Loss or Gain Due to Phase Separation Underground or During Ascent to the Sampling Point: Modes of Identication and Correction
Water in conned basins is characterized by high temperature, pressure, and dissolved gas concentrations. With the formation of a vapor or steam phase, helium is preferentially transferred into the gas phase, along with atmospheric Ne, Ar, Kr, and Xe. At the same time, the residual water is depleted in the noble gases. An example from the Great Artesian Basin is given in some detail: The samples were collected by the same eld team that provided samples for the work of Torgersen and Clarke (1985), our samples being collected in helium-tight glass tubes with spring-loaded high-vacuum stopcocks at their ends. The noble gas concentrations are seen to vary over a wide range (Fig. 14.2). Percent retention of atmospheric Ne, Ar, Kr, and Xe was calculated compared to 15 8C air-saturated recharge water (Fig. 14.3). Retentions as low as 16% are seen, indicating gas was lost. In contrast, cases with over 100% retention are observed, indicating gas was gained. These signicant changes in gas concentrations are not surprising, as the conned waters of the Great Artesian Basin are rich in CO2 and

Table 14.2 Discordant Groundwater Ages (years) in the East Midlands Triassic Aquifer, U.K.
Well Far Baulker 2 Ompton 3 Halam 3 Markham 3 Grove 1 Newton 1 Newark 1 Tritium * 15 * 40



Hydraulic 30008000 500014,000 500014,000 600016,000 20,00056,000 21,00060,000


25 220285 240320

02000 15005000 04500 35007000 700011,000 23,00028,000 > 29,000

6 10 hydraulic age 6 10 hydraulic age

Source: Data from Andrews et al. (1984).


Chapter 14

Fig. 14.2 Noble gas concentrations in water samples from the conned part of the Great Artesian Basin, with well numbers (following Mazor and Bosch, 1992b). The concentrations of atmospheric Ne, Ar, Kr, and Xe and of nonatmospheric He vary over a wide range, preserving the relative abundances as in air-saturated water at 15 8C (ASW 15 8C). A distinct enrichment of nonatmospheric (radiogenic) He is seen, correlated to the concentration of the atmospheric noble gases.

Helium-4 and Argon-40 Dating


Fig. 14.3 Percent retention of the atmospheric noble gases of the Great Artesian Basin samples included in Fig. 14.2 (compared to air-saturated water at 15 8C at sea level). Signicant gas losses are seen. (From Mazor and Bosch, 1992a.)

methane and attain temperatures of over 90 8C. Hence, samples collected at the (free-owing) well head are likely to lose gases during ascent, and gas separation may also occur underground as a result of pressure drops related to the intensive abstraction. The separated gases, forming gas pockets or compartments, are tapped by some wells, producing water enriched by noble gases. The original helium concentration in the conned water can be reconstructed by dividing the observed concentration by the fraction of gas retained, as calculated from the accompanying atmospheric gases. These corrected helium concentrations, plotted as a function of the distance from the recharge area (Fig. 14.4), reveal a reasonable correlation, which provides conrmation of the reliability of the corrected helium values. The observation of older groundwaters in the deeper parts of the Great Artesian Basin should not be mistaken as indicating inward ow. The older ages are in good agreement with the evolution of a subsidence basin the inner parts are buried and disconnected from the groundwater throughow regime for longer time periods.


Chapter 14

Fig. 14.4 Helium concentration (corrected for gas losses) as a function of distance from the recharge area along two transects through the Great Artesian Basin (following Mazor and Bosch, 1992a). The good correlation provides a positive check on the validity of the corrected helium data, as the deeper inland groundwater must have been trapped earlier.

14.11 Internal Checks for Helium Ages

A number of internal checks is available in specic case studies: . Good correlation of He concentration with 14C ages, as obtained for Blumau (Fig. 14.5), the Bunter sandstone in eastern England, or at Uitenhage. This check is limited by the half-life of 14C to rather recent shallow aquifers. In addition, this correlation can be taken as an approval of the deduced age only if absence of mixing is demonstrated. Good correlation with depth of connement, as seen for the Great Artesian Basin (Fig. 14.4), and as indicated by Andrews et al. (1984) for the Bunter sandstone aquifer.

Helium-4 and Argon-40 Dating


Fig. 14.5 4He concentration14C age correlation in the Blumau wells. (Following Mazor and Bosch, 1992a; data from Andrews et al., 1984.)

Good correlation with local depth, as seen in Blumau, the Bunter sandstone aquifer of eastern England, the Stripa granite in Sweden (Fig. 14.1), and in other examples included in Table 14.1, or good correlation with temperature, as seen at the Molasse Basin in Austria and the Great Artesian Basin in Australia (Fig. 14.1). Positive correlation of radiogenic helium and radiogenic 40Ar concentrations provides another check, observed in the geothermal elds of Larderellow, Italy (Mazor, 1979b), Yellowstone and Lassen Volcanic (Mazor and Wasserburg 1965), or Cerro Prieto, Mexico (Mazor and Truesdell, 1984). Agreement with the geological setting. The obtained groundwater age should be between the age of the aquifer rock and the age of the conning rocks.

14.12 The Issue of Very Old Groundwaters

The occurrence of old and even very old groundwaters, with ages up to 108 years, seems plausible in light of the local geological and hydrological histories of most deep basins. Much interest is to be found, in this context, in the results reported by Zaikowski et al. (1987) for deep Permian and Pennsylvanian brine aquifers at the Palo Duro Basin, Texas. The researchers found 90,000590,000 6 108 cc STP He/cc brine, and computed water ages in the range of 100300 million years, comparable with the age of the host rocks. Marty et al. (1988) observed in 1600- to 1850-m-deep Jurassic limestone aquifers of the Paris Basin up to 90,000 6 108 cc STP He/cc water, and calculated ages of 10140 million years, with a grouping around


Chapter 14

70 million years. This may well be the age of the water entrapment due to tectonic events that disconnected the system from its former drainage system.

14.13 Conclusions
The accumulation of radiogenic helium in conned groundwaters is mainly determined by the duration of water entrapment. Applying the data available on uranium and thorium concentrations in the host rocks and rock:water ratios, reliable, though semiquantitative, dating is possible in the range of 104108 years. Interference of helium diffusion from rocks outside the aquifers seems to be negligible because diffusion, if dominant, would tend to cause waters in different deep conned systems to have similar helium concentrations, but nature reveals in these systems values that range over ve orders of magnitude. The diffusion coefcient of argon is orders of magnitudes lower than that of helium. If diffusing helium is substantially added to conned water, but practically no argon diffuses into the aquifer, then no correlation is expected between radiogenic 4He and 40Ar in water samples collected at different parts of a groundwater system. The data on the joint occurrence of helium and radiogenic argon in conned water systems are scarce, but if such a positive correlation turns out to be common, it will further demonstrate the limited interference of helium diffusion in dating groundwater with helium concentrations. Contributions of mantle helium (mainly via magmas and waterdominated uids) may be detected and corrected by 3He:4He ratios. In order to date groundwaters, they have to be studied for possible mixing of waters of different ages. Helium concentrations should be applied for the calculation of meaningful ages only for nonmixed water or for reconstructed end members. Observed helium concentrations should be applied for water dating only in conjunction with the ANG, to correct for gas losses or gains. Internal checks are necessary for reliable water datingfor example, correlations of helium concentration with distance from the recharge area, water depth, temperature, or concentration of accompanying radiogenic 39 Ar.

14.14 Summary Exercises

Exercise 14.1: Study Fig. 11.26. Take the average helium concentration in group C as 26 6 108 cc He/cc water, and assume that the hosting rocks contain 2 ppm U, 2 ppm Th, the density of the rocks is 2.5, the rock:water

Helium-4 and Argon-40 Dating


ratio is 10, and the helium emanates from the rocks to the groundwater by a coefcient of 0.8. Applying the age equation, calculate the age of the groundwater. Does it seem reasonable in light of Fig. 11.26? Exercise 14.2: Sort the isotopic groundwater dating methods into decaying and cumulative methods. What are the advantages of each group? Exercise 14.3: How can the radiogenic helium be sorted out of the total helium measured in a sample? Exercise 14.4: On what arguments is it claimed that most of the produced radiogenic helium is released from the rocks and dissolved in the associated groundwater (i.e., the helium emanation coefcient is close to 1)? Exercise 14.5: Which mechanisms may cause losses of helium from sampled groundwater? How can we correct for these losses so that groundwater dating is feasible? Exercise 14.6: How can the patterns seen in Fig. 14.1 be understood in terms of the parameters controlling radiogenic helium contribution to groundwater? Exercise 14.7: Figure 14.2 incorporates a large body of noble gas data obtained from a huge subsidence basin. What can be learned from the reported noble gas ngerprints? Exercise 14.8: How was the data plotted in Fig. 14.2 transferred into the data plotted in Fig. 14.3? What patterns are observable in the Fig. 14.3?


15.1 Scope of the Problem

The glacial phases were events of extreme climatic conditions, manifested by a signicant increase in the global snow cover. By how many degrees was the local ambient temperature lower? What were the temperatures in the intermediate warmer phases? How abrupt were the climatic changes? Were there any phases of temperatures higher than the current ones? Answers to these questions will help us understand global climate dynamics. This topic is of much interest in connection with the discussion of possible climatic changes induced by anthropogenic activity such as release of CO2 and other greenhouse gases, release of dust and aerosols, changes in the ozone layer, deforestation, and desertication. Knowledge of natural temperature uctuations is essential in order to properly interpret uctuations in the temperature record available for the last century. Are they in the range of the natural noise, or are they outstanding and alarming? The concentration of the atmospheric noble gases dissolved in groundwaters, coupled with the dating of the respective groundwaters, provides a most valuable method to reconstruct paleotemperatures. The work done so far in this eld by various researchers (section 13.8) demonstrates the applicability of the method and thus opens a most promising eld of research. The future of this eld encompasses several tasks:


Paleo-Inputs and Water Dating Interrelations


. . . . .

Development of a technique to securely collect the water samples at specied depths in boreholes in order to prevent gas losses during ascent Routine collection of the auxiliary data needed for proper interpretation of the noble gas temperatures and isotopic dating Development of strategies to select the best sampling sites, for example, preference of stagnant (naturally capsulated) groundwater systems Global coverage of the sampling locations Application of paleo-input functions in the nal calculations of both the temperatures and water ages

15.2 The Need to Reconstruct Paleo-Input Values

Practically all computations discussed in this book so far are based on data measured in the eld, combined with certain coefcients and certain assumptions pertinent to the nature of the studied system: for example, the soil d13C value applied to correct the measured 14C value that is applied in the groundwater age calculation (sections 11.6 and 11.7). This soil d13C value is dependent on the type of growing plants, and these are climatically controlled. Thus applying a local present-day d13C value to water that contains only 10 pmc is improper. During the age that is indicated by the low 14C concentration, a signicantly different climate may have prevailed, and therefore a different plant community predominated, along with a different soil d13C value. A second example: The 36Cl:Cl ratio in local precipitation is dependent on, among other parameters, the distance from the sea. Thus applying the present local 36Cl:Cl ratio to calculate the age of groundwater may be wrong if the shoreline was located at a signicantly different distance. A third example: At certain geological and hydrological setups located in low lands, one can conclude that the local unconned groundwater system is recharged through a porous aerated zone, resulting in slow inow. In such cases the concentration of the atmospheric noble gases reects the average local ambient temperature (section 13.6). However, a deeper groundwater in the same site may be old and was recharged during glacial times when the snow lines were substantially lower and closer. At that time, recharge may have been mainly from snowmelt, and the concentration of dissolved atmospheric noble gases may reect a temperature that is close to the snowmelt temperature, rather than the average ambient temperature (section 13.8). A fourth example: The recharge altitude of an unconned water system is, under suitable conditions, reconstructed from the composition of


Chapter 15

the stable isotopes (the altitude effect; sections 9.89.10). The relevant formula is locally calibrated by measurements of springs of known recharge altitudes. However, ancient groundwater may have been recharged during a different climate, expressed by a different ambient temperature and a different recharge altitude as a result of a different snow line altitude. Thus the current coefcient of the altitude effect cannot be applied to old groundwater, and the respective paleo-coefcient has to be estimated.

15.3 Stagnant Systems as Fossil Through-Flow Systems

Stagnant groundwater systems are fossil through-ow systems that subsided into the zone of zero hydraulic potential (section 2.13, Fig. 2.14). The deeper stagnant systems became hydraulically sealed and isolated by overlying sediments that accumulated as subsidence continued (section 2.14, Fig. 2.16). Stagnant groundwaters are, in a way, samples that were naturally collected in the past and kept underground in closed system conditions. It is up to us to locate them and incorporate them in the global paleoclimate survey networks. The resolution of groundwater dating (e.g., by 14C) in through-ow systems is reduced by dispersion and other ow-induced disturbances, such as deviation from piston ow. In this respect stagnant systems are advantageous because they carry the age signal of the time of burial with no further dispersion effects.

15.4 Screening of Data for Samples of Last Minute Mixing of Groundwaters of Different Ages
Mixing of different groundwaters is always a possibility. Data from a sample that is mixed from different water sources are meaningless for both the dating of the water and the paleoclimate reconstruction. For example, a water sample from Baden, Switzerland, revealed 6 TU and only 7 pmc (Mazor et al., 1986). This set of data makes no sense because it means the water has a low age (post-bomb) and a high age (several half-lives of 14C) at the same time. The Baden sample is an example of a mixture of very young water (post-1954) and very old water (>30,000 years). Any two age indicators that have different half-lives can serve to identify mixed water samples. A second example is a well at the Lachlan Fan, Australia. It tapped conned water in Pliocene rocks, and revealed 36 pmc (indicating an age of about 1 half-life, about 6000 years) along with a 36Cl:Cl ratio of 78 6 1015,

Paleo-Inputs and Water Dating Interrelations


which is signicantly lower than the ratio reported for the active recharge area (36Cl:Cl ratio of 170 6 1015), indicating a much older age of about 1 36 Cl half-life, or about 300,000 years. Clearly the accompanying dD and d18O values of such samples are a mixture too, not reecting the composition of the young water or that of the old water, and the same holds true for the noble gas concentrations, ion concentrations, or concentrations of other age indicators. Data from mixed groundwater samples are misleading if applied for paleoclimate reconstruction or dating, hence the importance of screening data prior to their interpretation in terms of paleoclimate and age. The mentioned examples of contradicting tritium and 14C concentrations, or 14C and 36Cl concentrations, provide a clear indication that one deals with a mixture of waters. However, in many cases of mixed water samples, the age indicators are not that contradicting (e.g., mixing of two pre-bomb waters with 0 TU, or two waters older than 30,000 years with 0 pmc), and other methods for screening mixed water samples are needed, such as variations in ion concentration, observed in samples periodically collected from the same spring or well, or mixing lines obtained in ionic scatter diagrams of water samples collected in many sources at the same area (sections 6.6 and 6.7). In some cases the composition of the intermixing water end members can be retrieved and applied for dating and reconstruction of paleoclimate. Application of data of samples of single (nonmixed) groundwaters is always preferable, and in order to identify them the concentration of the various age indicators must always be identied, and chemical analyses of repeatedly collected samples are needed.

15.5 Paleohydrological Changes 15.5.1 Mode of Flow of Recharged Water in the Aerated Zone
Recharge through a porous medium is relatively slow, and the water owing down to the saturated zone undergoes two important processes: . . Partial evaporation and transpiration from the uppermost region, the former process inuencing the stable isotope composition. Constant temperature reequilibration, resulting in water entrance into the saturated zone at the temperature prevailing at the base of the aerated zone.

The temperature prevailing at the base of the aerated zone equals the local average ambient temperature if the aerated zone is at a depth of at least


Chapter 15

15 m. At greater depths heating by the geothermal gradient is added. In contrast, recharge intake through fractures and karstic conduits is fast, and . . No evaporation takes place from the upper aerated zone, preserving the isotopic composition of the recharged precipitation water. The water enters the saturated zone with a memory of the temperature prevailing during the recharge season.

Thus the nature of the recharge intake of a studied paleowater has to be dened by comparison with the present nature of the relevant recharge zone. The effect in terms of noble gas paleotemperatures can be demonstrated by an example from northern Israel: The average temperature in the rainy winter season is about 10 8C lower than the average annual temperature. This effect has been observed in noble gas temperatures of recent (tritium-containing) groundwaters that reected the average annual temperatures in springs fed by porous aerated zones, in contrast to about 6 8C lower noble gas temperatures obtained for karstic springs fed by winter rains and snowmelt water (Herzberg and Mazor, 1979).

15.5.2 Sea Level Changes

Water levels in the oceans were lower by over 150 m during the ice ages, and similar water level uctuations occurred in lakes and inland seas due to climatic changes and tectonic events. The sea level changes inuenced the near-shore regions in the following ways: . . . . The depth of the water table increased with the lowering of the sea level and decreased with the rise in the sea level. Hence, the depth of the aerated zone varied with the changes in the sea level. The intensity of the respective hydraulic gradient varied. The depth of karstic activity changed, forming new paths of preferred ow. The rate of chlorine fallout, determining the paleo-input value of the relevant initial 36Cl:Cl ratio (needed for 36Cl-based groundwater dating) could vary from the value calculated (Bentley et al., 1986 a,b,c), or locally measured, in recent groundwaters (Mazor, 1992b).

15.5.3 The Special Case of the Drying Up Event of the Mediterranean Sea
Since the 1960s more and more reports have been made describing the occurrence of deep Miocenian paleochannels detected in Mediterranean

Paleo-Inputs and Water Dating Interrelations


countriesin Africa, the Middle East, and Europe. The great depth of the paleochannels made it clear that the Mediterranean was, at that time, thousands of meters lower. Deep sea research drilling conducted in the Mediterranean Sea encountered gypsum among the bottom sediments, which is also exposed at the surface in Sicily. Gypsum is precipitated out of seawater whenever it is evaporated to less than one-third of its initial volume. Thus the nding of Messinian (Miocene) gypsum at the bottom of the Mediterranean Sea indicated that the sea was closed and highly evaporated, lowering its water level by 2000 m or more, as compared to its present level. Rock salt was found as well, and this material is precipitated from seawater only by evaporation to less than 10% of the initial volume. Finally, a bed with fresh water fossils was also encountered, indicating the sea was entirely locked at the Strait of Gibraltar, disconnecting it from its water supply from the Atlantic Ocean. So the entire Mediterranean basin dried up for a while, and then the strait was reopened and the sea lled up again. This is perhaps the most dramatic sea level uctuation during the late geological periods, dwarng in comparison the sea level changes during the glacial periods. The hydrological consequences must have been enormous: . . . . The water table in the surrounding countries must have dropped by hundreds to thousands of meters. The paleohydraulic gradient changed continuously, a fact that has to be taken into account in hydraulic calculations of the ancient groundwater ow velocities. The depth of the aerated zone increased accordingly, inuencing, for example, the noble gas recorded intake temperature (sections 13.7 and 13.8). The surface waters incised the landscape, forming deep channels that were lled with new terrestrial and marine sediments as the seawater rose again. These deep paleochannels serve, according to the nature of the lling sediments, either as potentially preferred ow paths and preferred underground drainage systems or as hydraulic barriers. The sea itself turned saltier, and the former offshore terrains that became exposed were covered with evaporitic salts. These two features must have increased the salt transport to the land (counteracting the effect of the receding shore) and changed the chemical composition of the sea spray to brine-spray.

As a result of the mentioned processes, slightly saline groundwaters must have formed in the surrounding continents during the regression of the Mediterranean Sea and during its relling. The increase in the salinity of


Chapter 15

those groundwaters must have stemmed from the mentioned increase in the amount of arriving sea spray, and of an expected drop in the amount of rain as a result of the drying up of the Mediterranean Sea. As the level of the recovering sea rose, the terminal base of drainage also rose. As a result, newly formed groundwater covered old groundwater. The older groundwater was submerged and turned stagnant as it was buried in the zone of zero hydraulic potential (section 2.13, Fig. 2.14). Thus one might expect that relatively saline old groundwater will be encountered in boreholes beneath the active through-ow zone, or base ow, in the coastal plains of the Mediterranean Sea. This is indeed intensively observed in Israel: boreholes that penetrate 30100 m below sea level in various parts of the coastal plain encounter groundwaters with 500700 mg Cl/l (Fig. 15.1). The composition of this more saline groundwater is characterized by less sodium and more calcium, as compared to seawater composition (i.e., in the direction of groundwater formed from sea spray of evaporitic nature). Overpumping of the shallow fresh coastal plain groundwater resulted in salinization to a degree that forced shutdown of wells.

15.6 Paleoclimate Changes 15.6.1 Changes in the Recharge Season: Possible Amplication of the Temperature Change Recorded by the Noble Gases
A relatively small drop in the average temperature during the Ice Age could cause a shift of the rainy season from summer rains to winter rains. Such a change in the recharge season would not affect the noble gas based paleotemperatures in the case of groundwater recharged through a porous aerated zone of a thickness of greater than 15 m, that is, enough to average out the seasonal and annual temperature variations. However, the change in the recharge season would result in an amplication of the temperature change recorded by noble gases in the case of fast percolating water through a thin or conduit-dominated aerated zone. In such systems the noble gas concentrations reect a temperature that is between that of the rainy season, or snowmelt, and the average annual temperature (Herzberg and Mazor, 1979). Effects of this nature should be borne in mind when addressing an inconsistency between reconstructed oceanic and continental temperatures, as pointed out by Stute et al. (1995a). The authors reported a temperature decrease of about 5 8C during the last glacial maximum, as recorded by noble gases in groundwaters at several locations in temperate countries, whereas the corresponding temperature decrease of the ocean surface was

Paleo-Inputs and Water Dating Interrelations


Fig. 15.1 Suggested formation of slightly saline groundwater, found in the Mediterranean coastal plane of Israel. (a) The lling up of the basin of the Mediterranean Sea as a result of the reopening of the Strait of Gibraltar: intensied sea spray of evaporitic nature prevailed, resulting in saltier rain and saline groundwater (open arrows). (b) The present Mediterranean Sea (open to the Atlantic Ocean), characterized by a higher sea level (bringing the ancient saline groundwater to below the terminal base of drainage, and thus making it stagnant), less sea spray, and formation of fresher groundwater (black arrows) overlying the ancient saline groundwater; a well producing fresh groundwater is marked. (c) Overpumping causes local lowering of the level of the fresh water table, resulting in lateral encroachment of remnants of the ancient saline groundwater, causing salinization of a coastal well.


Chapter 15

only about 2 8C, as indicated by oxygen isotope measurements on foraminifera and fauna abundances in deep sea sediments (section 13.8.3).

15.6.2 Changes in the Role of Snowmelt as a Recharge Agent

During colder climates the snow lines were lower, in extreme cases by up to 1000 m, as mentioned in section 13.8.3. This inuenced . . . The role of snowmelt in the recharge of a studied paleowater, relevant to the understanding of obtained noble gas based paleotemperatures, as discussed above. The altitude of the area of recharge, relevant to the altitude effect, taken into account in stable isotope paleoclimate deductions (section 9.8). The altitude to be applied as paleo-input in calculating noble gas temperatures. For example, a change of 200 m in the altitude of the recharge area implies a nearly 2.5% change in Xe solubility, equivalent to about 1 8C in the noble gas temperature calculation (section 13.2).

15.6.3 Type of Plant Community that Grew in the Ancient Recharge Zone
The type of plant community that grew in the paleorecharge area is relevant to the d13C input value, applied to correct the measured 14C concentration in order to correct for waterrock interactions (sections 11.6 and 11.7). Plant communities in the ice ages were exposed to colder climate, generally drier air, and a distinctly lower concentration of CO2 in the atmosphere. These parameters could cause the growth of plants that produced different (more positive?) d13C values in the soil air, as compared to the plants growing at present in the recharge area. This necessitates a different (smaller?) correction of the measured 14C in order to calculate the initial 14C concentration in a studied paleowater.

15.7 Selecting Sites for Noble Gas Based Paleotemperature Studies

In order to get noble gas based paleotemperatures that represent the average annual temperatures, study areas should be remote from past snowmelt recharge areas, and they should include only systems that received recharge through thick enough aerated zones in which porous ow dominated. On the other hand, the seasonal variations that accompanied the climatic

Paleo-Inputs and Water Dating Interrelations


changes of the past are best retrieved from groundwaters that were recharged through thin aerated zones or karstic domains and were located near former snowmelt recharge zones.

15.8 Stages of Data Processing

The data processing has to be done in stages. The data have to be screened for possible mixings of water from different aquifers, and only data from single aquifer samples, or values deduced for end members, should be applied in the following stages. Calculation of an approximate water age, applying the present-day input functionssuch as initial 14C concentration in the recharged groundwater and initial d13C value of soil CO2; initial 36Cl:Cl ratio in the recharged water; location and altitude of the present base of drainageand the respective present hydraulic gradient should be made. With the crude age one can estimate the paleoenvironmental conditions in terms of glacial or interglacial period, sea level, distance of paleorecharge area from the seashore, season of major recharge, altitude of the former water table, former evapotranspiration intensity, or the type of plant community that prevailed at the studied paleorecharge site. These considerations should lead to the selection of the pertinent paleo-input functions. One must then recalculate a more precise age for the studied groundwater, applying the deduced paleo-input functions. Final reconstruction of the paleoclimate conditions, based on the recalculated ages can then be done.

15.9 Summary Exercises

Exercise 15.1: An observation well, Curiosity 1, is located 3 km from the coast in a region of temperate climate. The well head is at an altitude of 15 masl, and water was sampled in a marine limestone aquifer from a depth of 105 m. A 14C-based age of 17,000 + 3000 years was deduced, and the d13C value was 8.1%. Another observation well, Curiosity 2, has been drilled 20 m away to a depth of only 18 m, and it reached water of a recent 14 C age and a d13C value of 8.3%. Discuss the past and present hydrological setup of the study area. Exercise 15.2: Following the conclusions stated in the answer to Exercise 15.1, is there a need to apply a correction to the deduced water age because the plant community could be different from that during a previous climate?


Chapter 15

Exercise 15.3: Can there be some doubt on the validity of the 14C-based age? What other parameters have to be measured? Exercise 15.4: Is there another way to identify possible mixing of different waters as a result of corrosion of the casing of a deep well (or mixing along a fault plain in the case of a spring)? Exercise 15.5: In light of the information discussed so far, is the Curiosity 1 well a good candidate for a study of noble gas based paleotemperature? Explain. Exercise 15.6: What type of temperature will the atmospheric noble gases in the deep well reect?


~~~~~~~~ Case Studies Are the Essence of Natural Systems Research

each one

Adds to Our Understanding


Renes the Working Hypotheses ~~~~~~~~


16.1 Scope of the Problem

Large-scale human operations carried out on the surface of the Earth include ever-increasing intervention in groundwater systems. All uses of water result in an increase in dissolved components, all used water has to be disposed of somewhere, and all disposed water eventually reaches existing water reservoirs: lakes, rivers, groundwater, and the ocean. Hence, an intrinsic part of water use is water contaminationthe addition of components that were not there before. Water quality control is, thus, an integral part of water production and consumption and, in the same way, water monitoring and tracing of pollutants is an integral part of the hydrochemists eld work. Monitoring of contaminants is somewhat like troubleshooting, but each contamination case study also has a scientic aspect, because each pollution case serves as a large-scale tracing experiment. The tracing of pollutants complements the methods presented in section 6.5, which is devoted to the establishment of hydraulic interconnections, the basic premise that underlies most groundwater models. The use of articial tracers introduced into groundwater systems for direct tracing of hydraulic interconnections is limited to wells that are tens of meters apart, and in karstic systems articial tracing may reach a few kilometers. For larger-scale experiments enormous quantities of tracers are needed, and these are costly and rarely authorized by the local health authorities. Pollution from a landll, waste dump, sewage disposal, factory efuents, or pesticide storage are all threatening. It is our challenge to use

Detecting Pollution Sources


such cases as large-scale tracing experiments, and to use each catastrophe to improve our understanding of the hydraulic underground plumbing. In essence, contamination monitoring and pollutant tracing are special cases of the general topic of water mixing, hence the emphasis placed on the detection of mixing of different water types, identication of end members, and calculation of mixing percentages (sections 6.4, 6.6, and 6.7). The mixing in contaminated water systems is twofold: . . Introduction of the contaminants into uncontaminated water. Introduction of specic properties of the water, which serves as a carrier for the contaminants, that may differ from the characteristics of the threatened groundwater system.

Examples of these include irrigation water that is partially evaporated and becomes enriched in deuterium and 18O, providing a signature that differs from the local groundwater into which the irrigation water carries fertilizers and pesticides. Water used by industry often comes from rivers or surface reservoirs with atmospheric tritium concentrations and enrichment in the heavy isotopes of hydrogen and oxygen, whereas threatened groundwater may be devoid of measurable tritium and have a light isotopic signature. In the deciphering of contamination problems all the tools of the hydrochemist come into play: many parameters have to be measured, repeated sampling is needed to understand the dynamics of the systems, and large amounts of data have to be processed.

16.2 Detection and Monitoring of Pollutants: Some Basic Rules 16.2.1 Prepollution Database
Lets begin the discussion with a question: 240 mgNO3/l have been detected in a farm well, much above the permissible concentration for domestic water. What should be done? Two steps are needed: (1) notify the local population of the nding and (2) search for the source of the contaminant. The rst step in the search is to establish the time when the pollutant arrived, and, in a case like nitrate, to nd out whether it is from a local natural source or a manmade phenomenon? When a pollutant is detected, all contamination sources should be considered. Knowledge of the pollutant arrival time may eliminate some suspected sources that started to operate at later dates, and helps narrow the list of possible sources of contamination. Hence the need for historic data (section 7.5). This information may be gathered from archives at local


Chapter 16

authorities, obtained from the well owner or found in published reports. The recommendation to collect historical data as a basic part of every pollution investigation sounds trivial, but in reality it is only partially followed. The need for a prepollution database is a major incentive for regional hydrochemical surveys that are performed periodically.

16.2.2 Identication of Specic Labels in Potential Contamination Sources

Work on potential pollution sources requires a thorough knowledge of the composition of potential pollutants. Maximum parameters should be measured on every industrial efuent that leaves a factory and the uid that is formed in each landll. The parameters to be measured include temperature, pH, major dissolved ions, trace elements (mainly metals and metal compounds), organic compounds, and isotopic compositions of hydrogen, oxygen, carbon, sulfur, and nitrogen. To perform such analyses, special laboratories have to be contacted. In certain cases the main product may serve as the label, and in other cases the labels are supplied by accompanying compounds, which in themselves may not be poisonous.

16.2.3 Movement of Pollutants in the Aerated Zone

Most pollutants are released on the ground and have to pass through the aerated zone before they arrive at the saturated groundwater zone. The nature of the aerated zone must be well understood in each case. Aerated zones with dominating ow in pores may retard wastewaters and cause biological decomposition of part of the toxic components or absorption of toxic ions on clay particles. These protections are absent in areas of conduit-dominated recharge. Hence, knowledge of the ow regime in the aerated zone can help in assessing the inuence of potential contaminating agents. The mode of uid ow in the aerated zone may be changed by the hydraulic aspects of uid waste disposal. Constant release of large amounts of uids may cause a local rise in the hydraulic head. Coupled with chemical uidrock interactions, this may form new high-conducting conduits that can lead the contaminants directly into the saturated zone. In other cases, ne particles that come with the contaminating uids can clog pores in the aerated zone and reduce through-ow.

Detecting Pollution Sources


16.2.4 Importance of Very Sensitive Monitoring Techniques

The propagation of pollutants takes time, and their arrival in springs and wells is often gradual. In ideal situations the arrival of contaminating uids can be detected by changes in the concentration of one or several parameters that are measurable but not toxic. In such cases preventive measures can be started in time to prevent toxic contamination, hence the emphasis on the most sensitive measuring techniques, either of in situ measuring probes or of laboratory techniques conducted on collected water samples.

16.2.5 Importance of Extensive Hydrochemical Studies

Hydrochemical surveys that encompass many wells and springs in extended areas may locate water sources of exceptional compositions, possibly caused by manmade contamination. Such surveys may detect contamination long before any complaints are expressed by water consumers. The next step in dealing with water sources that reveal suspected contamination is comparison of the composition with historical data, as discussed above.

16.3 Groundwater Pollution Case Studies

A large number of groundwater pollution cases are never published. This is especially true for severe cases. Yet an ever-growing number of case studies are being published. Every hydrochemist should read as many of these papers as possible, as each provides examples of possible scenarios and possible modes of diagnosis and remedy. A selection of pollution case studies is reviewed in the following sections.

16.3.1 Nitrate Contamination Detected by Depth Proles

Pickens et al. (1978) worked on nitrate contamination in wells drilled in a shallow sandy aquifer. An NO3 plume was detected in carefully sampled depth proles (section 7.3), as shown in Fig. 16.1. The contamination was attributed to extensive use of nitrate fertilizers. Discussion. . The arrival of the pollutant was detected at a very early stage 12 ppm of NO3 being alarming but not threatening. . The nitrate signal would not have been seen on a pumped sample, as pumping would lower the NO3 concentration by its averaging


Chapter 16

Fig. 16.1 NO3 (expressed in ppm N) in a depth prole in a piezometer. A contaminated water plume is seen at a depth of 3 m. (From Pickens et al., 1978.)

effect; hence the advantage of depth proles was demonstrated in this case. The nitrate peak indicates higher water conductance in the 2.5 3.0 m zonea direct contribution to the understanding of local groundwater ow.

16.3.2 Oxidation and Reduction Zones in Groundwater Proles and Their Bearing on Nitrate Contamination
Anderson et al. (1980) worked on nitrate distribution in the Karup Basin, Denmark. Results of depth proles in two boreholes are shown in Fig. 16.2. Discussion. Nitrate is seen to decrease at a water depth of 8 m (15 m below the surface), whereas iron is low at this depth and rises beneath. This indicates the existence of an oxidizing zone in the upper 8 m of water and a reducing zone below. The nitrate was reduced by ferrous iron to N2, which was expelled into the atmosphere. The tritium data were most informative:

Detecting Pollution Sources Fig. 16.2 Depth proles of Fe, NO3, SO4, Cl, and tritium in two test holes, Karup Basin, Denmark. A sudden change is observed at a depth of 15 m (8 m below water table), explained as indicating the occurrence of an oxidizing regime above 15 m and a reducing regime below (see text). 345


Chapter 16

values up to 200 TU were detected in the NO3-contaminated upper water zone, indicating post-1963 (manmade tritium peak) recharge (the study was conducted in 1976). Thus fast-arriving recharge was demonstrated, supporting the hypothesis of contamination by locally used fertilizers. The investigators determined the soils capacity to contribute ferrous iron to the reaction. This value is needed to assess how long one may rely on this mode of nitrate decomposition and to predict when nitrication will become a problem if the use of excess fertilizers continues.

16.3.3 Water Salinization Due to Removal of Vegetation

Borman and Likens (1970) reported changes in the composition of water owing from a watershed caused by removal of vegetation at the Brook Experimental Forest, Hubbard, New Hampshire (Fig. 16.3). Discussion. The time of experimental removal of vegetation is indicated in Fig. 16.3. A distinct rise in nitrate and calcium was noticed, while no rise was noticed in an adjacent undisturbed watershed. Thus the increase in nitrate was clearly related to the removal of vegetation, which lowered the denitrication effect. The increase in nitrate and calcium was abrupt and occurred 5 months after the vegetation clearing, demonstrating a piston ow recharge. Studies of this nature are relevant to the inuence of deforestation and vegetation stripping by coal mining. Such operations may deteriorate the quality of local surface and groundwater. Thus such operations should be accompanied by hydrochemical monitoring before, during, and after operations.

16.3.4 Monitoring of Nitrate and Chloride in an Irrigated Farmland

Safnga and Keeney (1977) monitored Cl and NO3 in shallow wells near a farm in central Wisconsin. In Fig. 16.4, the results from a well in an area not irrigated by the farm (well 7) are compared with the results from wells located in the irrigated farmland (wells 8 and 9, the latter was situated in a less cultivated part). The farming intensity dropped after 1972. Discussion. . The NO3 and Cl concentrations were correlated to irrigation intensity, since no increase was observed in well 7, located in a nonirrigated area, and as seen by the drop in Cl and NO3

Detecting Pollution Sources


Fig. 16.3 Change in nitrate and calcium concentration in water owing from a watershed cleared of vegetation (thick line) and an adjacent watershed with preserved vegetation (thin line). The arrows mark the date of vegetation clearance. Nitrate and calcium increased, with a 5-month delay, indicating piston ow recharge. (From Bormann and Likens, 1970.)

. . .

concentrations with the decrease in irrigation between 1972 and 1975. The Cl and NO3 covaried, indicating a common source, which was found to be two fertilizers applied in constant proportions: a nitrogen-rich fertilizer and a potassium chloride fertilizer. The recovery of the water quality in 1975 indicated that no salts were stored in the ground. The rapid recovery also indicated that the irrigation water reached the local groundwater rapidly, changes being observed from month to month (Fig. 16.4).


Chapter 16

Fig. 16.4 Nitrate (dots) and chloride (circles) in groundwater of a well (no. 7) in a nonirrigated area, and wells (nos. 8 and 9) located in an irrigated area, Hancock Experimental Farm. Irrigation caused an increase in nitrate and chloride, caused by nitrogen and potassium fertilizers, the latter containing Cl (KCl). The quality of water was restored because of a decrease in farming activities. (From Safnga and Keeney, 1977.)

16.3.5 Pesticide Contamination

Lewallen (1971) studied a farmers well in Florida, USA. High DDT, DDE, and toxaphane concentrations were noticed shortly after well completion. The detected source was backll soil, brought from a location where pesticide materials were dumped. The soil of the backll and sediment accumulated at the bottom of the poorly cased well contained high pesticide concentrations. In the second half of 1967 the well was cleaned and a proper casing was installed, causing an immediate drop in pesticide concentration (Fig. 16.5).

Detecting Pollution Sources


Fig. 16.5 Pesticide compounds in a well in Florida. (After Lewallen, 1971.) Contamination was caused by pesticide-contaminated soil in the backll and in sediment washed into the well. Cleaning of the well and repair of the casing removed the contamination and the well recovered.

Discussion. . The contamination decreased signicantly after cleaning and casing of the well, although no change was introduced to the adjacent backll. Hence, the pesticides were xed on the soil. . No conduit-controlled ow of water occurred between the backll site and the well area. Possible ow through a granular medium retarded pesticide contaminants by xation to the soil. . Although the quality of the water in the particular well was restored, much potential danger remains in the region and the surface, and groundwater zones should be carefully managed and monitored.


Chapter 16

16.3.6 Large-Scale Industrial Fluid Waste Injection

Goolsby (1971) described a thorough monitoring project of a large-scale industrial waste injection project in Florida. The task was to inject uid waste at a rate of up to 500 m3/h and about 3 6 106m3/year. The uid composition was described as an aqueous solution of organic acids, nitric acid aminos, alcohols, ketones, and inorganic salts. Discussion. The injection site was selected because of geological and hydrological considerations (Fig. 16.6): . . . . A free surface sand and gravel aquifer was found to overlay two major conned aquifers of Floridian limestone, the three being separated by distinct clay layers. The water in the upper limestone aquifer contained 425 mg Cl/l, whereas the lower limestone aquifer contained 7900 mg Cl/l. Thus the two aquifers did not communicate hydraulically. The water of the lower limestone aquifer was nonpotable. In no place was the saline lower aquifer water seen to ascend to the surface.

Fig. 16.6 Generalized geological cross-section through southern Alabama and north-western Florida. An injection well penetrated the conned lower limestone aquifer. (After Goolsby, 1971.)

Detecting Pollution Sources


. .

The recharge area of the lower aquifer was about 120 km to the north. The nearest possible discharge area of the lower aquifer, the ocean, was about 160 km south of the selected injection area. Thus the injection site was remote from recharge and discharge points, and the injected aquifer was saline and isolated from the overlying aquifer.

Injection and monitoring systems. An injection well (A in Fig. 16.7), 500 m deep, was drilled into the lower conned limestone aquifer, and later a second well (B) was drilled 400 m west of the rst one. A deep monitoring well, 400 m south of A, was drilled into the receiving aquifer. A shallow monitoring well was drilled into the upper limestone aquifer, 30 m from injection well A. Hence, changes in the chemical composition could be monitored both in the receiving and overlying aquifers. Water levels recorded in the two injection and two observation wells are given in Fig. 16.7, along with the injection rates. The following observations were made: . The deep monitoring well responded with an increase in water level as a function of the rate (and pressure) of injection.

Fig. 16.7 Piezometric water levels in waste injection and monitoring wells, and injection rates in Florida. (From Goolsby, 1971.)


Chapter 16

The shallow monitoring well revealed no change in water level, indicating the upper limestone aquifer was not affected.

The calcium concentration in the deep monitoring well is given in Fig. 16.8. The following patterns were observed: . Although the waste uid was low in calcium (about 3 ppm), it was calcium tagged in the aquifer. This was actually expected because of the reaction of the acid waste (pH 5, and later pH 3) with the aquifer limestone. The rst front of injected waste arrived 10 months after commencement of the operation. The arrival of the uid in the 400-m-distant monitoring well was noticed by a marked increase in calcium (Fig. 16.8). At the beginning of 1966 the calcium concentration decreased in the deep monitoring well, a feature not well understood. In 1968 a previous neutralizing process was stopped, and the waste was injected with a pH of 3, resulting in a sharp increase in dissolved calcium in the monitoring well (Fig. 16.8). This indicated that limestone was dissolved at a high rate. The resulting karstication probably enhanced the movement of the waste in the aquifer.

. .

Additional chemical data are given in Table 16.1. As mentioned, the composition of injected waste was changed in the middle of 1968, when neutralization was dropped. As a result, the pH went down to 3.3 and the nitrate concentration went up. The deep monitoring well responded in the following way (Table 16.1): the October 1967 and May 1968 analyses

Fig. 16.8 Calcium concentration, deep monitoring well, 19631964, Waste Injection Projection, Florida. (From Goolsby, 1971.)

Detecting Pollution Sources Table 16.1 Composition (mg/l) of Waste and of Groundwater Injected wastes Nov 1967 Ca NO3 Na Cl COD pH 3.4 2420 610 82 5.2 AprDec 1968 (average) <20 5070 <1000 200 22980 5.3 Deep monitor well Oct 1967 168 2 3720 5700 6.80 May 1968 165 0 3720 5900 2355 7.00


Jan 1969 2350 5760 635 161 22100 4.75

Source: From Goolsby (1971).

showed high sodium and chlorine concentrations, revealing dominance of the original saline aquifer water. The percent wastewater was calculated by the investigators from the chlorine concentration in the monitoring well (5800 mg/l) and the initial chlorine concentration in the lower limestone aquifer (7900 mg/l): percentage injected water : 7900 5800 6100 26% 7900

In other words, up to May 1968 the chlorine-rich aquifer water was diluted by 26% with injected chlorine-devoid water. The newer, nonneutralized waste with pH 3.3 caused a remarkable change in the composition of the uid at the deep monitoring well: chlorine dropped to 160 mg/l, indicating the deep monitoring well was dominated by 98% injected water: 7900 160 6100 98% 7900 The rapid increase from 26 to 98% waste uid in the deep monitoring well indicated that the nonneutralized waste dissolved the aquifer carbonates and developed a highly conductive karstic system, which was very alarming in terms of waste disposal in the aquifer. During all this time no chemicals arrived in the upper monitoring well.

16.3.7 Short-Circuiting of Aquifers by an Abandoned Well

Jorgensen (1968) investigated a case of water quality deterioration in a municipal well at Avon, South Dakota. The city wells pumped the free water table aquifer of the Codell sandstone (Fig. 16.9). Well A had a signicantly


Chapter 16

Fig. 16.9 Geological cross-section, Avon, South Dakota. An old corroded well short-circuited the deep pressurized Codell aquifer and the shallow Dakota aquifer, contaminating the latter. (From Jorgensen, 1968.)

inferior quality. Pumping tests supplied the rst clue: during a pumping test a contribution of 48% from another aquifer was detected. Local intrusion of water from the lower conned Dakota sandstone aquifer (Fig. 16.9) was suspected, as its water was known to be saline and of a piezometric head that exceeded the water level in the phreatic Codell sandstone aquifer. Chemical compositions and temperatures for the undisturbed phreatic aquifer, the conned aquifer, and well A are given in Table 16.2. A glance at the table reveals that the properties of the pumping test sample of the deteriorated well are indeed between the properties of the water in the Dakota sandstone aquifer and the Codell sandstone aquifer. The percentage (x) of saline and warm Dakota sandstone water in the pumping test sample can be calculated (section 6.7), applying several parameters: By temperature: 14 18x 111 x x 0:43; or 43% By calcium: 11 15:24x 71 x x 0:48; or 48%

Detecting Pollution Sources


Table 16.2 Dissolved Ions (meq/l) and Temperature in Wells Near Avon, South Dakota Dakota sandstone water Temperature Ca HCO3 Mg Na K CO3 SO4 Cl 18 8C 15.2 2.7 4.7 4.0 0.51 0.0 16.8 2.6 Codell sandstone water 11 8C 7.0 4.9 3.5 19.6 1.04 0.0 21.6 3.4 Pumping test well A water 14 8C 11.0 3.6 2.3 18.7 1.05 0.0 25.2 2.8 % Dakota water in A 43 48 57

Source: From Jorgensen (1968).

By bicarbonate: 3:64 2:69x 4:911 x x 0:57; or 57% These calculated mixing ratios agree well with the value of 48% contribution from the deep aquifer, determined from the pumping test. A later inquiry revealed that in 1870 a city well was constructed only 6 m away from the deteriorated well. That well reached the conned Dakota sandstone aquifer, and water rose in it above the piezometric level of the phreatic aquifer. That well was capped 50 years ago. It thus seemed that the casing of the old well had failed, short-circuiting the two aquifers and creating a saline plume in the upper aquifer, locally deteriorating the water quality. The agreement between mixing percentages calculated by the pumping test, temperature, and Ca and HCO3 values supported the hydraulic short-circuiting hypothesis.

Discussion. What should be done? The old well should be plugged in order to restore the separation between the two aquifers. Following the discussed mode of calculating the percentage of saline water in well A, the data in Table 16.2 can be used to calculate the percentage of saline water in well A based on the other parameters: Mg, K, CO3, SO4, and Cl. It turns out that


Chapter 16

these parameters do not play the game: the mixing percentages deduced from Na, K, and Cl differ from each other and from the values obtained by the pumping test and temperature, Ca, and HCO3 measurements. What could cause this disagreement? Is the whole short-circuiting hypothesis erroneous? The answer is that because of the mixing of two such different waters, it is possible that secondary interactions took place, affecting some of the dissolved ions. An example for such secondary reactions in a disposed slaughterhouse efuent is discussed in section 16.3.15.

16.3.8 Contamination by Released Oil Brines

Fryberger (1975) described a case study of groundwater contamination by displaced oil production brines. In 1967 a farmer lost his rice crop near Garland City, southwest Arkansas, USA, because his well water became saline. An adjacent oil eld came into production in 1955, with an increasing amount of separated brine that had been diverted into a poorly lined evaporation pond that leaked into the local aquifer. The brine was subsequently recharged into the ground through an abandoned production well, but soon the casing became corroded and the brine again reached the local aquifer. Eventually a new recharge well was constructed.

Monitoring project. To monitor the brine contamination, 36 observation wells were drilled to different depths. Chlorine, regarded as best representing the brine, was measured, and the data served to produce a chlorine concentration contour map (Fig. 16.10). The spread of the lines indicates the water in the aquifer owed southward. A section showing chlorine distribution (Fig. 16.11) also indicated a southward ow. To get a more complete picture of the brine movement, a schematic compositional crosssection was prepared (Fig. 16.12). The results were plotted as a function of the distance of each observation well from the contamination center. The concentration of Cl, Br, F, Pb, Ca, Mn, Ni, and Al decreased in a pattern explainable by mixing, in various proportions, of contaminating brine and local groundwater. However, several dissolved ions revealed different patterns, indicating secondary processes occurred: . Iodine, iron, and zinc increased in wells over the concentrations in the brine or local groundwater, represented by the private (PVT) well. The researchers hypothesized that chemical displacement of ions coating the sand grains took place. This explanation is plausible for the iron alone. Hence, another explanation was

Detecting Pollution Sources


Fig. 16.10 Isochloride contours at the bottom of the alluvium aquifer, Gerald City. Flow to the south is seen. (From Fryberger, 1975.)

Fig. 16.11 A chloride concentration cross-section, Gerald City. Leakage from the brine evaporation pit is recognizable. The heavy brine accumulated above the shale aquiclude. (From Fryberger, 1975.)


Chapter 16

Fig. 16.12 Composition histograms (mg/l) of the brine pit of Gerald City and monitoring wells, arranged by increasing distance from the pit. A contamination gradient is observed from the brine pit toward the fresh water well PVT. (From Fryberger, 1975.)

. .

offeredthat the brine disposed in earlier stages had a different composition. Barium is seen in Fig. 16.12 to drop faster than chlorine in wells TW 11 and TW 20, indicating effective precipitation en route. SO4 is high in the private well and TW 20, indicating it is high in the local groundwater. The observed drop in SO4 concentration in TW 11 and TW 3 is probably due to consumption by barium precipitation.

Discussion. The term conservative is applied to dissolved ions that, except for mixing, take part in no other process. In contrast, nonconservative ions reveal changes in concentrations caused by mixing of two water types and, in addition, by waterrock interactions. Looking at Fig. 16.12, which ions

Detecting Pollution Sources


are conservative and which are nonconservative? Cl, Br, Ca, Ni behaved as conservative ions. In contrast, secondary reactions changed the composition of the water by exchange reaction with rocks, for example, with Fe and possibly Zn. Conclusion. Different ions travel at different velocities, the conservative ions moving fastest. The conservative ions are most helpful for the understanding of groundwater ow.

16.3.9 Contamination by Repressuring of an Oil Field

Wilmoth (1972) reported that a domestic well in Kanawha County, West Virginia, USA, contained only 32 mg Cl/l until 1967. This excellent water quality deteriorated because of brine injected into an adjacent oil well. Within 1 year the chlorine concentration rose to 1140 mg/l (Fig. 16.13). Operations were stopped and the chlorine concentrations decreased slowly, reaching a value of 450 mg Cl/l early in 1971, and the well could be used once more. The decrease in chlorine was caused by natural ushing of the water owing in the aquifer. A second case described by Wilmoth (1972) in the same country related to a fresh water aquifer near Wallace that contained 100 mg Cl/l. In late 1967 injection of brines, as part of subsurface operations in an adjacent oil eld, caused an increase to 2950 mg/l chlorine concentrations within 2 months. Operations were stopped and the water quality was soon restored, attaining concentrations of 190 mg/l after 2.5 years (Fig. 16.14).

Fig. 16.13 Changes in chloride in a contaminated well adjacent to an oil eld, Kanawha County. Fast response to brine injection in a nearby well was observed, as well as fast recovery after brine injection was stopped. (Following Wilmoth, 1972.)


Chapter 16

Fig. 16.14 Changes in chloride in a contaminated well adjacent to an oil eld, Kanawha County. Injection of brines into nearby wells caused a dramatic increase in chlorine, which was cured in 2 years. (After Wilmoth, 1972.)

16.3.10 Leakage from a Cooling Pond Monitored by Temperature Measurements

Andrews and Anderson (1978) applied temperature measurements to trace leakage from a cooling pond. The pond served two 500-MW electric power plants of the Columbia Generating Station, located on the oodplain of the Wisconsin River, near Portage, Wisconsin, USA. The cooling pond was constructed of 5-m-high dikes, covering an area of 200 ha. The bottom, a silty sand, was partially lined with bentonite. The area is a discharge zone of marshes and wetlands. The geology of the area was studied with 100 borings, the water table was monitored by 80 small-diameter observation wells, and heat proles were measured in 19 observation wells. Figure 16.15 provides an example of temperature data obtained in the extensive monitoring operation. The summer temperature peak reached well B (60 m from the pond) 60 days after it reached well A (3 m from the pond). Thus the water leaking from the pond traveled 60 m in 60 days, or 1 m/day. A network of 47 boreholes of 10-m depth were equipped with thermistors for extensive monitoring.

Detecting Pollution Sources


Fig. 16.15 Temperature variations in well A (4 m depth, 3 m west of the dike) and well B (2.5 m deep, 60 m west of dike). The summer temperature peak reached well B 60 days after it reached well A, indicating a ow velocity of 1 m/day. (After Andrews and Anderson, 1978.)

16.3.11 Contamination by a Coal Ash Pit

Andrews and Anderson (1978) studied the impact of a coal ash pit that served two 500-MW electric power generating units near Portage, Wisconsin, USA. Water in the ash pit differed in its composition from the local groundwater. Operation of the power plant began in May 1975, monitored by four wells that were constructed south and north of the pit dikes. Selected data are reported in Table 16.3 Discussion. From Table 16.3, it emerges that the data for 19721973 predated the operation of the power plant and reect the composition of the nonpolluted local groundwater. The variations in composition between wells A, B, C, and D reect natural uctuations in the local groundwater composition. For example, calcium occurred in the range of 13.9 to 31.6 mg/ l, and SO4 varied from 0.8 mg/l (well B) to 9.7 mg/l (well D). Bearing these variations in mind, it seems that . Ash pit water reached no well, considering potassium and magnesiumthe relatively high values observed exceeded the values in the ash pit water and must be due to some other reason (e.g., secondary waterrock interactions). Sodium indicates contamination in well A alone. Ca, SO4, and Cl indicate pollution in wells A and C.

. .

The conclusion from all observations is that the water reached wells A and C, located 1 m west and north of the pit, and no contaminating water


Table 16.3 Water Composition (mg/l) in Ash Pit and Monitoring Wells Near Portage West of the dike A, 1 m west 19723 1.2 2.2 13.9 11.1 5.4 3.4 9.2 8.5 16.9 9.8 18.5 4.5 6.9 13.2 21.6 14.7 10.5 6.5 1.2 3.6 31.6 20.3 0.8 4.49 0.75 3.5 28.8 22.0 0.2 2.64 0.5 4.0 24.3 16.9 0.1 5.0 2.4 10.3 54.7 4.3 36.0 10.5 1.7 4.3 18.8 17.3 7.7 2.8 19756 1977 19723 19756 1977 19723 19756 0.75 2.6 23.3 22.5 9.6 4.2 B, 75 m west Ash pit water C, 1 m north 1977 1.5 5.1 37.0 33.8 22.0 8.5

North of the dike D, 25 m north 19723 2.0 5.2 22.0 18.0 9.7 7.2 19756 0.75 3.1 22.6 18.8 9.3 3.2 1977 0.5 3.7 21.5 25.8 14.0 3.5

Ash pit water 2.3 10.2 77.8 10.6 44.6 10.6

K Na Ca2 Mg2 SO2 4 Cl

Source: From Andrews and Anderson (1978).

Chapter 16

Detecting Pollution Sources


reached wells B and D, located 75 m west and 25 m north. The contamination was restricted to the immediate surroundings only.

16.3.12 Fly Ash (Coal) Contamination

Cherkauer (1980) monitored groundwater near a y ash site, operating 8 years for the Port Washington Power Plant in southeastern Wisconsin, USA. The maps in Fig. 16.16 show the potentiometric surface contours and direction of ow, TDS, SO4, Ca, and HCO3, along with the positions of the monitoring piezometers. The ash leachate contained various metals that were not observed in the monitoring wells, except some iron.

16.3.13 Monitoring Leachate of a Sanitary Landll

Fritz et al. (1976) studied possible movement of leachate from a sanitary landll in Frankfurt am Main, Germany. In a preliminary search for suitable tracers it was found that the leachate leaving the waste disposal site was enriched in deuterium and 18O (possibly due to evaporation). The leachate was enriched by 1.52.0% of d18O, whereas the analytical resolution was + 0.1%. The site operated from 19251968, and about 1.8 6 107 m3 of garbage were deposited there. The underlying phreatic aquifer, built of quaternary sand and gravel, was biologically polluted. Samples were collected in test wells that penetrated the aquifer, at depths of 811 m. Samples were also collected from drainage ditches in the landll. Partial chemical data are given in Table 16.4, along with chemical oxygen demand (COD), reecting the concentration of organic matter in the polluted uid. The locations of the test wells and piezometric contours are given in Fig. 16.17 and 16.18, respectively. Discussion. Looking at the water table elevations (Fig. 16.18) and the analytical results (Table 16.4), which wells may be regarded as representing uncontaminated groundwater? Well 401 is upstream (Fig. 16.18), and on this basis alone should be uncontaminated. This is conrmed by the observation that the water in this well is lowest in Cl, NH4, COD, and TDS. Wells 404, 405, 406, 415, 416, and 417 are closest to the landll and in the groundwater ow direction (Fig. 16.18). Therefore, they should to be suspected of contamination. The data reveal that these wells, and additional wells that are located downow, are indeed contaminated. Of special interest (and warning) is the observation that different parameters assign a different degree of contamination to individual wells. For example, well 404 is most contaminated by Cl and COD but slightly less by NH4. To make this point clear, the wells are listed in Table 16.5 in


Chapter 16

Fig. 16.16 Data of a y ash site monitoring operation, southeastern Wisconsin. Upper left diagrams: Water table contours (masl), September 1978; dots mark locations of piezometers; heavy line marks the boundary of the lled area; dashed line marks surface drainage. Contours of dissolved ions are in mg/l. Right bottom: TDI changes in contaminated well (25) and uncontaminated control well (20/3). (After Cherkauer, 1980.)

Detecting Pollution Sources Table 16.4 Composition of Surface and Groundwater Near Landll Site, Frankfurt am Main Station no. 401 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 20 21 26 28 Cl (ppm) 19.3 2682 1806 1725 987.7 1670 26.0 73.1 168.9 43.1 14.6 11.7 1883 1610 719.3 40.4 1636 1713 61.2 920.5 SO42 (ppm) 122.5 867.3 89.5 990.5 285.8 117.1 48.1 131.3 224.7 82.4 45.6 40.5 137.2 313.4 217.1 35.6 214.3 211.5 126.1 127.9 NH4 (ppm) 0.16 244 1404 603 623 198 0.16 1.55 0.74 1.78 0.06 3.09 119 114 3.19 0.04 104 104 73.1 135 COD (ppm) 10 1310 1070 1310 460 880 8 4 46 29 8 24 960 810 305 25 820 765 375 520 TDS (by evaporation) (ppm) 256 9250 8670 7800 6700 5700 233 493 722 344 348 287 6950 6300 2665 551 5400 5400 2011 3350


Comments Groundwater Groundwater Groundwater Groundwater Groundwater Draws lake water Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Lake water Lake water Lake fed by ditch Ditch fed by groundwater

Source: From Fritz et al. (1976).

decreasing order of concentration of each contaminant. The relative order of the wells in the Cl column is seen to differ from the arrangements by SO4, NH4, and COD. Yet an overall picture is obtained: wells 404, 405, 406, 407, and 408 are clearly contaminated. There are several reasons that could explain the observed differences: . . . The sanitary landll is not homogeneous, and different parts seem to contain different types of garbage. The uncontaminated groundwater might have had slight differences of composition. Some of the ions could be retarded by soil components or exchanged with soil and rock, and these changes might differ locally.


Chapter 16

Fig. 16.17

Sanitary landll, Frankfurt am Main. (From Fritz et al., 1976.)

Fig. 16.18 Water levels (masl) in a shallow aquifer at a sanitary landll, Frankfurt am Main. (From Fritz et al., 1976.)

Detecting Pollution Sources Table 16.5 Monitoring Wells Arranged in Descending Order by the Various Tracers (after Table 16.3) Cl 404 415 405 406 408 416 407 417 411 410 412 418 409 401 413 414 SO42 406 404 416 407 411 417 415 410 401 408 405 412 409 413 414 418 NH4 405 407 406 404 408 415 416 417 414 412 410 411 401 409 413 418 COD 404 406 405 415 408 416 407 417 411 412 418 414 401 409 413 410


Where was the contaminating groundwater front? It was situated between the most distant wells that reveal contamination and the closest wells that reveal no contamination. Well 401 has been selected as representing the uncontaminated groundwater, as discussed above. Well 401 is emphasized in Table 16.5, and the wells listed below well 401 may be regarded as uncontaminated. By this approach it is seen that only two wells are uncontaminated, taking Cl as a tracer, whereas 7 wells are uncontaminated using SO4 as a tracer. Chlorine and COD were the most conservative (and therefore most sensitive) tracers in the Frankfurt am Main study. The importance of analyzing many parameters is hereby demonstrated. Later measurements may be limited to the established conservative, most sensitive tracers. Figure 16.17 shows that the landll is situated near two lakes and a pond, which have a possible inuence on local groundwater and need to be understood and taken into account in the interpretation of the pollution monitoring results. dD and d18O turned out to be most useful in this respect. The d18O data, given in Table 16.6, reveal three groups of values: 8.6% to 8.0%, 6.7% to 6.3%, and 3.0% to 2.0%. Can sense be made of these three groups, denoted by d18O (and dD)? Consult the map given in Fig. 16.17 and the following picture emerges:


Chapter 16

Table 16.6 Isotopic Composition of Surface and Groundwater Near the Landll Site, Frankfurt am Main

O (%) June 1975 8.5 8.4 8.6 8.5 8.6 8.5 8.0 8.4 6.2 7.3 7.4 6.9 6.9 7.3 4.4 4.5 5.3 7.8

dD (%) April 1973 55 55 43 46 32 31 24 29 41 June 1975 58 57 59 59 58 58 55 58 42 45 47 43 39 48 33 37 46 55 Comments Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Groundwater Draws lake water Lake water Lake water Lake water Lake water Lake fed by ditch Ditch fed by groundwater

Sampling point 401 409 410 411 412 413 414 417 418 404 405 406 407 415 416 408 20 21 21 23/24 26 26

Nov 1972 8.6 8.3 8.5 8.2 8.3 8.2 8.1 8.0 8.4 6.3 6.7 6.4 6.5 6.4 6.4 2.9 2.0 3.1 3.0 7.2 7.1

April 1971 8.2 8.3 8.6 8.6 8.4 8.5 8.3 7.8 6.5 6.8 7.1 7.0 6.6 6.7 4.0 3.5 3.7 4.0 3.2 7.0 7.2

Source: From Fritz et al. (1976).

. . .

The rst group, which includes well 401, is of uncontaminated groundwater. The second group is of polluted groundwater. The third group, including well 408, reects recharge from Draws Lake.

A second pattern, noticeable in the isotopic data of Table 16.6, is a systematic change to more negative values, seen in those wells that have been shown by their dissolved ions to be contaminated (Table 16.5). This demonstrates the progressive increase of water from the landll.

Detecting Pollution Sources


The d18O data have been used by the researchers to calculate the percentage of leachate water in each well, summed up in a map of the pollution plume (Fig. 16.19). The correlation between the isotopic data and dissolved ions has been checked in Fig. 16.20. Good positive correlations are observed between Cl, COD, and d18O, and almost no correlation is seen with NH4 and SO4. This supports the conclusion that Cl and COD (as well as d18O and dD) were conservative tracers.

16.3.14 Contamination by Highway Deicing Salt

Dennis (1973) studied the impact of a stockpile of 50,000 tons of salt used for highway deicing at Mars Hill, Indianapolis, Indiana. The salt was stored in 1966 and removed in 1968 because the local aquifer turned saline (several thousand mg Cl/l). The aquifer recovered gradually. In 1976 the water of most wells was potable, but traces of the contamination were still reected in an isochlor contour map (Fig. 16.21). This accident supplied interesting hydraulic information: it established the direction of ow at Mars Hill, and the observation that the wells recovered in 6 years indicates the aquifer is highly dynamic. A second case of contamination by road salt piles has been described for Monroe County, West Virginia (Wilmoth, 1972). Chloride concentrations in water of a 500-m-distant well (25 m deep) increased from 185 mg/l to 1000 mg/l in 5 years. The chlorine concentration rose to 7200 mg/l in

Fig. 16.19 Pollution plume, outlined by d18O, landll site, Frankfurt am Main. (From Fritz et al., 1976.)


Chapter 16

Fig. 16.20 Cl, COD, NH4, and SO4 as a function of d18O, landll site, Frankfurt am Main. Circles: November 1972; dots: April 1973. (From Fritz et al., 1976.)

response to an enlargement of the salt storage area. The salt piles were removed in 1970, and within 2 months the chlorine concentration decreased to 188 mg/l (Fig. 16.22). The extremely fast recovery indicates that the studied aquifer has a large through-ow.

16.3.15 Slaughterhouse Waste and Secondary Ion Exchanges in Soil

Mazor et al. (1981) studied contamination of groundwater by a slaughterhouse at Lobatse, Botswana. Sodium chloride, used to wash and preserve

Detecting Pollution Sources


Fig. 16.21 Mars Hill, 1973: location and isochloride contours (mg/l). Groundwater has almost recovered, but the salinity distribution still reected the southward direction of groundwater ow. (From Dennis, 1973.)

Fig. 16.22 Chloride in shallow groundwater, Monroe County. A salt pile caused severe contamination in a 500-m-distant well. The system recovered within 2 months after the salt pile was removed. (From Wilmoth, 1972.)


Chapter 16

Fig. 16.23 Chloride concentrations (mg/l) observed in wells (dots), Lobatse Botswana. High concentrations were observed near the slaughterhouse and close to the Peleng riverbed. (From Mazor et al., 1981.)

skins, was a major contaminant released with the slaughterhouse efuent. Preliminary studies revealed chlorine and tritium as the most conservative tracers in this case. The slaughterhouse used water from a dam, and this water had tritium concentrations that were signicantly higher than in the local groundwater. The location of the slaughterhouse and chlorine and tritium concentrations are shown in Figs. 16.23 and 16.24, respectively. Signicant contamination is seen in wells close to the slaughterhouse and along the Peleng riverbed, into which the efuent was released. Other wells reveal low chlorine and tritium values, indicating they remained unconta-

Detecting Pollution Sources


Fig. 16.24 Tritium concentrations (TU) observed in wells, Lobatse, Botswana. High values were observed in wells (dots) near the slaughterhouse and near the Peleng riverbed. (From Mazor et al., 1981.)

Fig. 16.25 Variations in dissolved ions in well P209, located on the slaughterhouse grounds, at Lobatse, Botswana, reecting the seasonal nature of the release of efuent.


Chapter 16

Fig. 16.26 Composition diagrams of wells at Lobatse, Botswana: uncontaminated wells (circles) and contaminated wells (dots). Sodium does not reveal an increase with TDI, but calcium and magnesium do, indicating sodium was exchanged for calcium and magnesium. (From Mazor et al., 1981.)

Fig. 16.27 Laboratory experiments: compositional changes in NaCl-rich industrial and domestic sewage after 170 days contact with soils of Lobatse, Botswana (Table 16.7). Sodium was exchanged for calcium and magnesium. (From Mazor et al., 1981.)

Table 16.7 Chemical Changes (mg/l) in NaCl-rich Industrial and Domestic Sewage Stored in the Laboratory with Soils of Lobatse, Botswana Description 1.2 1.0 1.1 2.0 0.51 0.46 48.9 46.8 47.9 4.0 3.9 6.9 52.6 54.4 51.1 4.7 4.0 3.4 3.6 3.9 5.5 6.2 6.2 9.4 K Mg2 Ca2 Na Cl 59.2 60.3 58.1 58.9 58.3 56.2 SO42 4.4 5.5 4.3 5.0 2.9 4.0 HCO3 4.2 2.2 0.33 0.46 0.24 0.33

Detecting Pollution Sources


Baseline a

Sewage efuent Sewage efuent stored 170 days (blank) 400 g soil (from well 1931 area), with 500 cm3 sewage efuent, stored 170 days 400 g soil (topsoil, near Geol. Survey) with 500 cm3 sewage efuent, stored 170 days 400 g soil (from 1.8 m depth, near Geol. Survey) with 500 cm3 sewage efuent, stored 170 days 400 g red soil (from well 1379) with 500 cm3 sewage efuent, stored 170 days

Source: From Mazor et al. (1981).



Chapter 16

minated. Contamination in the wells uctuated with time (Fig. 16.25), reecting the seasonal nature of the slaughterhouse output and demonstrating the immediate effect of contamination. Composition plots (Fig. 16.26) revealed an interesting pattern: chlorine in the contaminated wells was positively correlated to TDI, as expected from the NaCl disposal. In contrast, sodium revealed only a small increase in the contaminated wells and no correlation to TDI. This was compensated by increases in calcium and magnesium in the contaminated wells (Fig. 16.26). The explanation offered was that sodium was exchanged for calcium and magnesium upon interaction of the efuent with calcium and magnesium carbonates or with clays in the local soil. The observations at Lobatse were thus another case in which pollution served as a large-scale tracing experiment, checking a natural phenomenon. Because of its special interest, the exchange was checked in laboratory experiments in which the sewage efuent was stored with Lobatse soil samples for 170 days (Table 16.7). The results are plotted in Fig. 16.27, revealing a drop in sodium and gain in calcium and magnesium. Such exchanges are common and show that a contaminant released into the ground may cause pollution of groundwater by another contaminant.

16.4 Summary of Case Studies

Detection of sources of contamination and monitoring of waste disposal of all kinds are tasks that have to be handled with the highest standards and expertise. No case is the same as any previous case, so experience plays a major role. The case studies described in this chapter are a small assortmentjust to convey the nature of the job. A recommendation is to read and get familiar with as many case studies as possible. The ones published in professional journals have the advantage of being well presented and concentrating on the highlights. But most pollution research is summed up in bulky reports that can be obtained from relevant agencies. Such reports provide a more realistic picture of the difculties that have to be overcome, the huge amount of data accumulated, and the countless number of possible modes of data processing and problem solutions. Pollution detection and monitoring projects should be planned and conducted within the guidelines that were found useful for all hydrochemical studies (Chapter 7). To these should be added the requirement for specialized laboratories that analyze the specic compounds present in unusual wastes.

Detecting Pollution Sources


16.5 Summary Exercises

Exercise 16.1: Read again the nitrate contamination case study (section 16.3.1) and suggest how to proceed. What should be done next? Exercise 16.2: Section 16.3.9 deals with a case of groundwater contamination by injected oil brine. Figure 16.13 reveals that the chlorine concentration decreased quickly after the brine injection ceased. Is this full proof for complete restoration? Exercise 16.3: Looking at the composition of the water in the ash pit (Table 16.3), and bearing in mind the discussed observations on the rate of water movement (section 16.3.11), can the monitoring operations be stopped? Are there any other suggestions? Exercise 16.4: Study the data plotted in Fig. 16.16. What is your expert opinion?


17.1 Sustainable Development

Sustainable development means managing a resource in a way that it is protable without that resource being depleted. In regard to groundwater, sustainable development means Pumping that is limited to the volume of recharged water. In other words, it is groundwater exploitation that nearly equals, but never surpasses, the amount of groundwater that would be drained naturally into the ocean. Maintaining the natural recharge mechanisms and enhancing them. Preserving groundwater qualityavoiding deterioration by arrival of anthropogenic pollution or by pumping-induced intermixing with low-quality groundwater. Avoiding overpumping-induced cessation of groundwater drainage to the ocean, as it also means loss of drainage of salts and pollutants.

17.2 Man and Groundwater: A Historical Perspective

For hundreds of thousands of years man was limited in his activity to the immediate vicinity of available water sources, thus restricting his territorial distribution. The invention of water carrying vessels increased the radius of travel a little. With the passage to animal husbandry and farming in the Neolithic period, some 7000 years ago, the demand for water increased. This was the background for the development of the large river civilizations in

Sustainable Development of Groundwater


the Middle East, based on irrigation canals. In the vast semiarid areas that have no perennial rivers, wells were dug; and the Bible contains testimonies to their importance to the well-being of whoever had control of them. The city of Jerusalem is situated in the mountains in a region that is devoid of rivers or lakes, and from its founding, some 3000 years ago, it was dependent on the collection of rainwater and water brought in from springs (the local groundwater table was too deep to be tapped by wells in those days). In Europe, America, and other areas cities grew most commonly on the banks of large rivers, and until recently most urban water supplies came from dammed surface reservoirs. To overcome years of drought and cope with pollution of the surface waters, these cities incorporate in their supply systems an ever-growing number of wells, and their dependence on the groundwater resource is constantly growing. Groundwater exploitation has come a long way since the early days, when man derived water from shallow wells using a bucket and a rope, to the present use of powerful deeply submerged pumps. In ancient times wells were dug to depths of 12 m below the water table, and therefore water could only be skimmed. The wells were left to recover overnight. Thus in ancient times the exploitation did not cause a lowering of the natural water table. Today groundwater is often overpumped, resulting in signicant lowering of the local water table, on the order of up to tens of meters, making room for encroachment of saline water from the sea or from stagnant deeper aquifers. In addition, modern man heavily pollutes his environment to a degree that endangers groundwater. The demand for high-quality groundwater will steadily increase in the future, because of population growth and because of an expected rise in the living standard of the worlds population. This increased economic activity brings with it the danger of increased pollution of the groundwater. Pessimists see the situation as grim, and optimists see the tremendous challenge of proper management of the groundwater resource. It is in this nichethe challenge to optimally manage groundwater systemsthat the hydrochemist is called to play a key role.

17.3 The Concern Over Groundwater Quality: A Lever for the Demand of Clean Nationwide Management
The atmospheric system rapidly recovers after cessation of contamination, and the seashores rapidly recover whenever sea pollution is stopped. In contrast, certain types of nondegradable pollutants accumulate in ground-


Chapter 17

water systems, spoiling them for long periods of time. Some contamination of groundwater systems is irreversible in human time scales. In addition, cleaning up of ruined aquifers is an unrealistic mission, technologically and nancially, a lesson learned from large efforts invested in small-scale remedial operations all over the world. Because of this vulnerability of groundwater, it is important for the future of this resource that man switchs to clean management of all his enterprises. Environmental activities are so far mainly directed at cleaning pollution crises after they happen. The main current approach is to treat the symptomscleaning up contaminated sitesinstead of ghting the diseasethe making of pollution. It seems that future development can be reasonable only if pollution is considerably restricted. Every factory needs to treat its own waste, or switch to clean production processes; every municipality needs to treat its own sewage efuents; and the issuing of licenses for new factories should be conditioned on clean management that ensures that no pollutants that are harmful to groundwater are released. The outcry for clean management has to be led by groundwater specialists acquainted with the quality aspects of groundwater systems.

17.4 The Value of the Environment: An Essential Parameter in Economic Calculations

Clean management is often put off by economic considerations: If a certain chemical factory has to be fully clean, the products will be too expensive; if sewage treatment installations are required to be absolutely leakproof and covered by an appropriate monitoring network, they will not be protable; local landlls instead of centralized landlls may have environmental advantages, but may be more expensive to operate. This is poor and shortsighted thinking. In the name of short-term interests, groundwater systems are allowed to deteriorate, especially under circumstances in which observable harm is delayed for awhile. The value of the environment has to be an integral part of the equations applied to protability calculations. The value of the respective aquifer has to be taken into account in economic considerations. This approach will no doubt reveal that cleanly managed enterprises are protable, and all the rest are in the long run economic disasters. Evaluating the value of the relevant aquifers necessitates delineation of their extent, and this is in the realm of the hydrologists and hydrochemists eld of study.

Sustainable Development of Groundwater


17.5 Recharge and Its Controls

Upon reaching the ground, precipitation is divided into runoff and inltrating water. The latter is divided into water that is returned to the atmosphere by evapotranspiration and recharge that reaches the saturated groundwater zone. Agricultural activities, mining, dams, canals, roads, and buildings disturb the natural balance between these parameters of the water cycle. In semiarid and arid regions recharge of groundwater is a necessity, and it has to be preserved and even enhanced. In contrast, in regions with high precipitation and in certain urban areas in atlands, recharge may be in excess and has to be restricted. The processes involved in recharge control are numerous, with a delicate interplay between the natural processes and anthropogenic interventions. The following sections describe the most important processes.

17.5.1 Permeability of the Ground Surface

Sand dunes are highly permeable and water readily inltrates in them, resulting in minimal water loss by evapotranspiration, which is reected in a very low salinity and an isotopic composition that is as light as the composition of the local precipitation water. Soils have varying permeabilities, according to their clay content. The soils ability to take in water may be signicantly increased by desiccation cracks, animal holes, or plant roots (Fig. 2.3). Man enhances water intake by plowing. Anthropogenic pollution moves with the inltrating water. A profound understanding of the listed processes is essential in order to decide on pollution prevention measures.

17.5.2 Landscape Surface Morphology

Runoff is controlled by the landscape relief and the riverbed network. All earth-moving construction interferes with the natural setup, in some places arresting water and causing increased water intake and in other cases enhancing runoff. Agricultural terraces, plowing along elevation contour lines, and dams are the most common means by which man slows down runoff and enhances recharge. In contrast, drainage trenches are intended to reduce water intake and remove part of it as runoff. Man interferes with the water cycle by constructing mines, quarries, roads, railroads, and irrigation and transportation canals. Thus every construction project must be accompanied by careful planning to minimize damage to the groundwater system. In addition, monitoring to determine the hydrological outcomes should be an integral part of every construction project. Monitoring should


Chapter 17

include composition analyses and water table measurements. The results may be crucial in the identication of groundwater damaging obstacles.

17.5.3 Irrigation
Irrigation is a most noticeable manmade contribution to recharge. Irrigation is harmless, or even positive, as long as the following conditions are met: . . The soil and rocks in the aerated zone are of good permeability, making room for efcient drainage to below the root zone. The local through-ow groundwater system is well drained to the sea.

Under such conditions irrigation can go on uninterrupted for centuries. However, under poor drainage conditions irrigation can be harmful. Irrigation water is exposed to intensive evapotranspiration that returns pure water back to the atmosphere but leaves behind all the dissolved compounds. Thus the recharged irrigation water is enriched in dissolved components compared to the supplied water. In many regions the water for irrigation is supplied from local wells. Thus, in cases of poor drainage to the sea, water may be cycled between the irrigated elds and the local pumped aquifer, causing salts to accumulate and deteriorate local groundwater quality. Groundwater deterioration in poorly drained terrains is enhanced by accumulation of fertilizers and pesticides, washed into the local groundwater system. This process is further aggravated by irrigation with treated sewage water, which contains residual dissolved ions and organic materials. To what extent these processes take place can be established by monitoring to detect changes in the chemical composition of the groundwater (appearance of compounds typifying the irrigation activity) and its isotopic composition (arrival of highly evapotranspired water).

17.6 Overpumping Policy: The Through-Flow Systems

What effects a signicant lowering of the water table by intensive pumping will have is a major question in groundwater exploitation policy. A number of processes warrant consideration in each case of recommended overpumping. The role of each of these processes has to be estimated in each case, based on knowledge of the local system and ongoing monitoring.

Sustainable Development of Groundwater


17.6.1 Seawater Encroachment

Salinization is often observed in heavily pumped coastal wells. This observation is commonly based solely on chlorine concentration data, and is almost always attributed to seawater encroachment, which is made possible because of overpumping. The real cause of salinization has to be investigated in each case with the aid of complete chemical and isotopic analyses. Seawater intrusion is usually limited to a distance of 12 km from the sea, but it varies. The depth at which seawater-induced salinization occurs increases with the distance of the well from the sea. The invading seawater may have direct hydraulic interconnection with the open sea, or it may originate from a stagnant compartment of seawater that was trapped during past hydrological conditions. The latter case will be recognizable because of the old age of the saline water and by deviations from the present seawater composition, reecting seawaterrock interactions.

17.6.2 Encroachment of Stagnant Saline Groundwater

Saline groundwater occasionally invades inland wells of high-quality groundwater because of overpumping. An example of the occurrence of such saline paleowater, and its encroachment into overpumped wells, has been described for the coastal plain of the Mediterranean Sea (section 15.5.3). The occurrence of shallow stagnant groundwater has been little investigated, but it might become better known thanks to the increasing number of observations of salinization in inland wells.

17.6.3 Cessation of Drainage to the Ocean

The bulk of the through-owing groundwater is drained by lateral base ow to the ocean (section 2.13.1; Figs. 2.142.16). Under natural steady-state conditions all the recharged water is discharged, guaranteeing that all the dissolved components are drained as well. The groundwater cycle functions in the following mode: distilled water is pumped by the sun into the clouds and precipitated on the continent, where part of it is recharged underground. Groundwater becomes enriched in dissolved salts from sea spray and from interaction with rocks along its ow course, but ultimately it is drained back into the ocean, the sea acting as a major sink for dissolved compounds. This steady state can be disturbed by lowering of the water table to an extent where the lateral base ow to the ocean is interrupted. From this moment on the salts accumulate in the groundwater system instead of being drained into the ocean. The same holds true for contaminants; they accumulate in the groundwater system as well.


Chapter 17

The need to preserve some degree of seaward drainage has to be taken into account in groundwater management considerations. At the least, periodic drainage to the sea has to be maintained.

17.7 Optimization of Pumping Rates in the ThroughFlow System

Authorities who operate wells are constantly tempted to pump as much as possible, either to supply ever-increasing demand or to save the drilling costs of more wells at more distant locations. Overpumping occurs whenever the amount of pumped water is greater than the amount of recharged water that reaches the respective part of the groundwater system. Overpumping is evidenced by a signicant lowering of the local or regional water table. Study of the compositional changes of the groundwater as a function of the lowering of the water table can reveal the nature of the secondary processes that occur. The following points have to be taken into account in the pumping rate considerations: . Overpumping is a mining operationit provides a one-time, nonrenewed amount of water (once the decided minimum water table has been reached, all subsequent pumping is limited to the amount of recharge). In undisturbed systems pollutants reach the base ow zone and do not penetrate into deeper (below sea level) stagnant parts of the system. Thus the deeper stagnant parts below through-ow systems may serve as a strategic reserve of clean water. Lowering of the water table may ruin this reserve because it lets pollutants reach the deeper parts of the system. Overpumping makes room for the encroachment of seawater (close to the coast) and deeper saline groundwaters (in certain regions). Overpumping reduces the seaward drainage of dissolved compounds and pollutants.

. .

17.7.1 Setting of Red Lines and Monitoring

A clear pumping policy has to be formulated for every region in accordance with its hydrological structure. It seems useful to sum up the accepted policy in terms of red lines of maximum tolerable lowering of the water table and maximum tolerable concentrations of water quality key parameters. These parameters have to be monitored routinely. Electric conductivity and water table may be monitored continuously by instruments placed in observation wells or pumping wells. In the latter case, the respective

Sustainable Development of Groundwater


dynamic water table will be measured. The monitoring network has to be organized to issue real-time warnings to the well operating agency, a topic further discussed in section 18.2.

17.8 Optimal Utilization of the Groundwater Resource

A basic rule of economic geology states that an ore deposit should always be exploited so that its highest potential value is harvested. This rule is applicable for groundwaterthe many different qualities and modes of emergence call for careful marketing evaluation and rational planning of the exploitation of this basic commodity.

17.8.1 Pricing by Quality

Groundwater is used for a large number of different purposes, and each consumer has a specic minimum quality demand. Yet water is often supplied with a higher quality than needed, for example, to certain types of industry or agriculture. If the price of water is set according to its quality, some consumers may prefer lower-quality water, relieving the pressure on the high-quality resource. This policy implementation is based on hydrochemical expertise.

17.8.2 Groundwater-Fed Sources as Assets of Nature

Cold and warm springs, oases, waterfalls, and wetlands are a few examples of groundwater-fed assets of nature. In the hasty drive to exploit groundwater, these presents of nature are often destroyed. However, these features should be protected and preserved as remnants of the unspoiled systems of the earth. Besides their aesthetic merit, these assets have a high economic potential, in the frame of national parks, recreation areas, or central attractions in resorts. Spotting the best candidates for conservation and securing their preservation are in the realm of the hydrochemists.

17.8.3 Stagnant Systems: A Strategic Reserve

Stagnant groundwater systems, especially the pressurized and hydraulically isolated ones (sections 2.13 and 2.14), call for a management policy that is entirely different from that developed for through-ow systems (section 17.6). The rock compartments that host stagnant groundwater are isolated from the surface and have no drainage. These stagnant groundwaters have the following characteristics: . . They constitute a nonrenewable resource. They are protected from anthropogenic pollution.


Chapter 17

They possess an excellent storage capabilityfor durations reected in the old age of the waters (104106 years).

Many of the known artesian groundwater systems are used for irrigation, or occasionally for space heating. Being regarded as a cheap commodity, they are often wasted. However, in light of their special qualities, pressurized stagnant groundwaters are a precious resource that should be developed with concern and planning. Pressurized stagnant aquifers with good-quality water should be preserved for times of need; severe droughts, large-scale pollution accidents, or nuclear catastrophes. In times of crises, a few weeks may pass before it is clear which of the ordinary wells are contaminated. In this critical period stagnant aquifers can supply pollution-free water. Hence, selected highquality pressurized aquifers should be drilled and equipped for emergency water extraction. Pressurized stagnant aquifers with slightly saline water should be preserved for similar reasons, because their water may be useful for largescale decontamination activities, for domestic and industrial needs in times of shortage, and for future desalinization, especially in remote inland regions. The practice of exploiting artesian systems has produced a large number of depressurized stagnant aquifers that are at present of no use. Such aquifers, which supplied high-quality water, can be reused by reinjecting fresh water to create pollution-immune underground water reservoirs. The different management strategies recommended for through-ow systems and stagnant systems demonstrate the importance of correctly identifying the hydrological regime of every exploited groundwater system.

17.9 Groundwater Aspects of Urban and Statewide Development Planning and Management 17.9.1 Surface Coverage by Roads and Buildings
A signicant quantity of rain and snow water comes off of the roof of every house. Prior to erection of the building, this water reached the ground and contributed to the local recharge. Thus buildings make the ground impermeable. In ancient times this water was collected in cisterns and used for the household, but this wise practice has to a large extent been abandoned. Similarly, paved roads cover the Earths surface with an impermeable layer. In extreme cases the pavement entirely closes in the trunks of the trees that grow along the streets, leaving no space for water

Sustainable Development of Groundwater


inltration. The impermeable coverage of cities may exceed 90% of their area. The result: the region is deprived of its former recharge and the local groundwater table drops, especially if pumping from local wells continues.

17.9.2 Street Runoff Mitigation

The rain and snow water reaching the urbanized areas is transformed into street runoff. Unless it is specially managed, street runoff causes a number of problems: . . . Flooding of streets at peak rains Flooding of basements and rst oors Flooding of the existing sewage system

The common way to cope with street runoff is to construct a special drainage system, the water being evacuated to the sea, a lake, or a river. In this way the comfort of the citizens is maintained, but the region is deprived of its original recharge (previous section). The latter effect is of importance in semiarid and arid regions, since in these regions water supply is mostly from local wells. There is another solution. Water from roofs can be diverted to adjacent open areas or gardens. The streets and pavements should be built with local slopes toward trees growing along the streets, and the streets should slope toward adjacent small and large public gardens and other open spaces. In this way a signicant portion of the rain and snow water can be diverted back into local recharge, and the negative effects of street runoff will be eased. The rest of the runoff should be recharged into the ground by spreading over special inltration elds or via reinjection boreholes.

17.9.3 Raising of the Water Table Due to Sewage Inltration or Irrigation

Many of the worlds residential areas have no central sewage systems, and the domestic sewage goes to septic tanks or to toilet pits. The resulting effects are . . A general rise in the local water table, sometimes to an extent that building foundations are damaged and basements are constantly damp. The local groundwater quality is deteriorated to an extent that it is unhealthy and nonpotable.


Chapter 17

The remedy in such cases is clear: construction of central sewage collection and treatment installations and acquiring a supply of water from wells that are outside the residential area. The ultimate goal is to reach the state described in the previous section, namely, a well-organized street runoff mitigation system beside a central sewage system. The moment this stage is reached, groundwater extraction from local wells can be renewed. Monitoring of the groundwater condition is essential until all the remedial steps are undertaken. There are different levels on which the monitoring can be performed. But, means being limited, any monitoring is better than none. The results of the monitoring are crucial in order to avoid immediate health disasters, make the authorities and the public aware of the urgent need for the remedial measures, and prepare the database needed for the optimal planning of the remedial measures.

17.9.4 Location of Urban Landlls, Sewage Treatment Plants, and Industrial Zones
Landlls, sewage treatment plants, and factories can be planned and managed with high environmental standards. The location decisions of such undertakings have to ensure the safety of the groundwater. For this reason, the following surveys and studies are essential: . The groundwater systems of the planned area and its immediate surroundings have to be identied in terms of through-ow systems (the area may belong to several local drainage basins) and stagnant systems (unconned and conned). Each groundwater system has to be characterized in terms of its depth and aerial extension, water composition, isotopic composition, concentration of water age indicators, and arrival of specied pollutants. The ow direction in each of the local through-ow systems has to be established. The thickness of the aerated zone and the nature of its soil and rocks have to be established in terms of the lithologies, prevalence of conduit ow or porous ow, and absorption capacity. An updated data bank must be maintained that includes as much old (historical) data as possible.

. . .

Based on the outcome of these detailed studies, landlls, sewage treatment installations, and factories should be placed according to the following considerations:

Sustainable Development of Groundwater


. . .

At the downow end, to ensure that arriving contaminants do not reach local wells Above sections of soils and rocks of the aerated zone that are richest in clay and other absorbing rocks Away from operating wells or surface water supply installations (lakes, dams, or rivers)

17.9.5 Irrigation Optimization

Irrigation is a major water-consuming activity that results in signicant release of water into the ground. The outcomes are crucial to the groundwater, both quantitatively and qualitatively. Irrigation affects groundwater in the following ways: . . . . Irrigation adds water recharged into the unconned through-ow system. The recharged irrigation water is enriched in dissolved ions as a result of evapotranspiration activity, a feature also reected in enrichment in the heavier hydrogen and oxygen isotopes. The irrigation recharge water is often enriched in fertilizers, pesticides, nitrate, and other compounds that are formed in the soil zone. Irrigation water transports pollutants from the surface down into the throughow system.

The impact of irrigation on groundwater can be mitigated in the following ways: . . . . . . . Irrigate at night in order to signicantly reduce evaporation, thus reducing the quantity of consumed water and reducing evaporation-induced water salinization. Irrigate by methods that reduce evaporation (i.e., avoiding sprinkling and ow in ditches), but do not increase local soil salinization. Install sensors to monitor the water content in the soil root zone to automatically control irrigation to amounts that are just enough to saturate the root zone or slightly beneath it. Use closed greenhouses. Avoid crops with extra high water demands. Develop and install sensors for fertilizer compounds in order to restrict the use of fertilizers in the root zone, with no leftovers to be washed into the groundwater system or to accumulate above it. Develop and install sensors to determine the concentration of specic pesticides on plants in order to optimize their application.


Chapter 17

17.9.6 Agricultural and Urban Use of Treated Efuents

Sewage efuents can be reclaimed in quality grades that are perfectly suited to irrigation purposes. In an increasing number of countries, water shortage makes irrigation with treated efuents attractive. This practice is feasible, provided a number of precautions are taken: . . . . The quality of the treated efuent must be routinely monitored, and the use of contaminated batches must be avoided. The local groundwater quality must be routinely monitored to ensure its quality is not lowered. The soil condition must be routinely monitored to ensure that its physical properties are not harmed, for example, by too high doses of sodium that may cause particle dispersion. All the precautions recommended in the previous section for irrigation are implemented.

Treated efuents are also suitable for public gardens, golf courses, playgrounds, forests, and other public open areas.

17.9.7 Groundwater Vulnerability Maps: A Questionable Approach

Maps that delineate the vulnerability of various regions to their groundwater deterioration as a consequence of planned human activity have become a fashionable tool tailored for planners. The basic idea sounds good: hydrologists take existing geological maps and translate them into groundwater vulnerability maps. The most common type of map is of the time predicted for the arrival of pollutants in the local groundwater. The criteria applied to prepare such maps include . . . Rock types; classied by their permeability: the less permeable, the longer is the predicted time span until pollution will arrive. Thickness of the aerated zone; the thicker it is, the longer are the pollutants predicted to be retarded. The nature of the inltration system: if porous, the movement of pollutants is assumed to be slow; if conduit controlled (karstic), pollutants will arrive fast.

There are several major problems with the described approach. First, the geological maps are prepared by stratigraphic units, and the lithology has to be inferred. In any case, stratigraphic units include, in most cases, alternations of various rock types, often with a wide range of permeabilities. It is almost impossible to translate a geological map into permeability units.

Sustainable Development of Groundwater


Second, it is almost impossible to quantify the terms fast arrival and slow arrival of contaminants. In some vulnerability maps the legend is divided into intervals of arrival time (e.g., within 3 years, within 20 years, and later than 20 years). Third, the nature of the inltration setup (depth to water table, porous or ssured medium) varies on a small scale, and there are no hints to it in geological maps. The information has to be derived from other sources, which are rarely at hand. A major problem with the preparation of groundwater vulnerability maps is anchored in the basic question of whether the time of arrival of contaminants is at all a base to assess vulnerability. Is fast arrival better or worse than slow arrival? Fast arrival may in fact be advantageous, because the outcry against the pollution act will be immediate, and dilution with through-owing ground-water will be relatively efcient. Late arrival postpones the protest, and in the meantime pollutants can accumulate in the aerated zone to a degree that can be built up, causing unreversible damage. The issue of vulnerability maps deserves serious consideration. The topic is presented here in order to draw attention to the problems and to warn against uncriticized use of such maps by planners. The warnings and solutions have to be provided by hydrochemists.

17.10 Summary Exercises

Exercise 17.1: Overpumping at coastal plains occasionally draws the water table beneath the average sea level. The result is cessation of groundwater drainage to the sea (section 17.6.3). Is that not a good result, as no groundwater will be lost to the sea? Exercise 17.2: Is fossil stagnant groundwater renewed? Has it any advantage over active through-owing groundwater? If so, how shall stagnant groundwater be used? Exercise 17.3: What is the essence of the concept of sustainable development of the water resource? Exercise 17.4: How can street runoff be mitigated? Exercise 17.5: Cities have industrial zones that may well pollute the local groundwater system. Has this danger any bearing on urban planing?


18.1 Drinking Water Standards

The quality of drinking water is kept safe by a set of regulations that dene the maximum concentration of an extended list of compoundsthese are the drinking water standards.

18.1.1 Considerations Involved in Setting the Drinking Standards

Issuing regulations for safe drinking water may at a rst glance seem as a simple and straightforward task. In reality it turns out to be rather complicated and a continuous operation. Let us have a glimpse at the process: . . . Drinking water standards dene the maximum tolerable concentration of a long list of dissolved compounds. Assumed life-long consumption. The drinking standards are set with the assumption that local inhabitants will drink the discussed water all their life. Hence, the standards are very strict. The lowest concentration of each compound observed to cause poisonous symptoms is studied on animals in the laboratory and tted to the human biomass. In addition, experience with people who have suffered from drinking of a certain water is applied. Safety factor. The lowest concentration of a compound observed to be poisonous is divided by a safety factor, often 100 or even 1000.


Water Quality, Monitoring, Education


Unpolluted water is safe. Observation: almost all the water in nature is safe for drinking, and the rare cases that are not safe are nontasty, e.g., very saline waters, or they have a bad smell, e.g., of H2S. So nature has its safety measures, and tasty water is nonhazardous. The danger of manmade pollution is that poisonous materials will reach the water with no accompanying bad taste or smell to warn us. Composition of nonpolluted water overrules the safety factor. The above-described procedure results occasionally in a situation such that the drinking standard would be so low that a substantial part of the available nonpolluted water would be declared nonpotable. In theses cases the standard is set slightly higher than the observed natural concentration. This is one of the reasons that drinking standards differ between countries.

18.1.2 List of Regulated Standards

A long list of compounds is treated by the drinking water regularities. They include the following groups of compounds: . . . . . . . . . . . . . Inorganic chemicals (e.g., antimony, arsenic, asbestos, barium, cadmium, chromium, lead, mercury, seleniumaltogether around 16 compounds) Organic chemicals (over 50 listed compounds) Volatile organic compounds Nitrate Gases (e.g., H2S, CO2, CH4) Pesticides Detergents Microorganisms (bacteria, viruses, algae) Turbidity (by sediment particles or microorganisms) Radionuclides (alpha particle emitters, beta particle emitters, radium-226, and uranium) Disinfectants and disinfection by-products Compounds causing cosmetic effects (e.g., skin or tooth discoloration) Compounds causing esthetic effects (e.g., taste, odor, color)

The values and lists of regulated parameters have to be acquired from local authorities, as they differ from one country to another and are frequently updated.


Chapter 18

18.1.3 The Practical Meaning of the Drinking Standards

The health aspect. In a local newspaper there was once an alarming caption stating that in a certain spring the measured alpha emitting radioactivity was found to be twice the drinking water standard. In order to judge what twice the standard value means let us remember that the standard has been established under the following procedure: The lowest concentration at which health damage has been observed divided by a safety factor that often is 100 or more. Thus it is the order of magnitude that counts. Hence, a concentration twice the standard is still safe, especially if the consumption is for a short time. Yet the standards have to be strictly observed in the ongoing supply of the drinking water. What should be done in cases where standards are exceeded? If the concentration of one or several compounds in a water source is found to exceed the standard values, the following steps have to be undertaken: (1) the reason for the change has to be found, and the respective operations have to be undertaken; (2) the water source has to be monitored more often and closely watched; (3) it has to be decided in advance at which concentration values exploitation as drinking water has to be ceased.

18.1.4 Additional Water Types for Which Standards Are Needed

So far we have discussed the drinking water standard. Similar regulations are needed for water for other uses, e.g., bottled water, public bathing, irrigation, treated sewage water, etc.

18.2 Water Monitoring Networks

Water monitoring stations are well marked and well studied locations at which water properties can be measured continuously or periodically, and representative water samples can be collected for laboratory analyses. Examples include sites along rivers, lakes, ponds, sea shores, piezometers, wells (both operating and observation wells), and springs.

18.2.1 Aims of Monitoring Networks

Water monitoring networks are organized in order to provide . . Base data to which future results may be compared Results of detailed studies of selected monitoring stations

Water Quality, Monitoring, Education


. . . .

Reproducibility and use of standard procedures of data collection Data collection in reasonable frequencies Awareness of arrival of contaminants Data for conceptual and mathematical modeling

18.2.2 Surveys of Inventories Related to the Planning and Running of Water Monitoring Networks
A monitoring network can be planned only if its objectives are dened, and for that the inventory of the monitored area has to be known in the following terms (Figs. 18.1 and 18.2): . . . . . . Types and intensity of plant coverage Types of rock exposures and soil coverage Potential pollutants, e.g., types and amounts of fertilizers used; modes and intensity of irrigation; and location of sewage facilities, landlls, feedlots, abattoirs, or factories Main river and its tributaries Other water bodies and sources, e.g., lakes, swamps, ponds, dams, sea shores, springs, wells Projects of relevance, existing and planned

Each survey of related inventories should be summarized in a report that contains . . . . . . Map of geological outcrops (stratigraphy and rock types) and soils Land use and potential pollutants map and water inventory map that includes the surface water system, springs, and wells (Figs. 18.1 and 18.2) Data table including ow or discharges, temperature, and chemical and isotopic compositions of all measured points Technical data, e.g., lithological proles, description of casings, location of perforations Compilation of the data and understanding of the water systems Management recommendations

18.2.3 Selection of Network Stations

Network stations must be chosen to secure proper representation of a list of relevant features . . . Representative types of exposed rocks and soil. Different physiographic units, e.g., high and low regions. Different types of land use, e.g., farming, pasture, urban.


Chapter 18

Fig. 18.1 Example of a land use map needed for the proper planing of a water monitoring network.

Water Quality, Monitoring, Education


Fig. 18.2 Water inventory map that includes the water monitoring stations and all the existing wells. The latter may be checked whenever alarming pollution has been observed at any of the regular monitoring stations. Lines AA1 and CC1 are suggested directions of geologicalhydrological cross-sections to be prepared for the monitoring network reference book.


Chapter 18

. . .

Major potential sources of pollution. Installations belonging to water management projects, e.g., dams, irrigation channels. With regard to a river system, it is of interest to monitor water quality along the main river and establish the salt and pollution contribution by each tributary. This is a promising way to detect pollution sources in due time.

Accessibility and other practical points should be taken into account. Financing will in most cases be limited. Hence, optimization is needed along the following variables: . . . . . . Number of monitoring stations. Location of stations (e.g., close to main roads or remote). Frequency of measurements. Parameters measured at the eld or at laboratories. Number of automated (continuous recording) stations. Stations with high ow or discharge rates are in most cases more important than stations with a low output.

18.2.4 Thorough One-Time Investigation of Every Station

Every surface and groundwater station of the network should be thoroughly studied in order to understand the hydrological system of each station (what is measured?) and determine the parameters that should be included for each station in the routine monitoring. Points to be studied are 1. Land uses and potential pollutants. From this will be concluded special ions and components to be analyzed in specialized laboratories (e.g., ions included in relevant fertilizers, relevant pesticides, local landll and sewage efuents, and industrial wastesall of which may be site specic). This stage of the investigation is crucial because Contaminants are useful hydrological tracers. The established concentrations will provide reference values for future monitoring. The results will help to dene which special analyses should be included in the routine monitoring measurement at each station. 2. Physical parameters, such as temperature, ow rate, pressure or discharge, and dimensions including depth.

Water Quality, Monitoring, Education


3. Dissolved compounds. In an ideal situation the one-time investigation should address the entire list of drinking water standards. In any case, the analyzed ions should include the major ions (Na, K, Ca, Mg, Cl, HCO3, SO4, NO3, Br); dissolved oxygen, CO2, and methane; isotopic composition (e.g., deuterium, 18O, 13C) and age indicators (e.g., tritium, 14C, 36Cl and 4He; the last should be included for waters that are estimated to be old). 4. Depth proles should be attained in lakes, dams, and wells by logging the temperature, electrical conductivity, pH, and dissolved O2. In addition, water samples have to be collected along the prole for laboratory analyses. 5. The following information has to be acquired during the drilling of new wells in the network: Speed of drilling (a lithology indicator). Cuttings washed from the drilling uid and kept along with depth documentation. Loss of circulation, indicating possible karstic or other preferred ow paths. Any indication of encounter of a new water stratum should bring the drilling to a stop and proper measurement and sampling of that water.

18.2.5 Monitoring During Pumping Tests

The importance of a thorough follow-up of pumping tests has been addressed in section 4.6, and we will get here a further look into the needed action. Pumping tests are an intensive intervention in the local water regime, as the intense pumping reduces water pressures locally. As a result, water from adjacent aquifers, or water compartments, may encroach. Thus every pumping test should be accompanied by continuous measurement of temperature and electrical conductivity, and samples should be collected along the test for laboratory analyses. Basically, two types of outcome are experienced: . Water temperature and conductivity remain constant during the pumping test. In such cases only the sample collected before the pumping test was started, and the last sample should be analyzed at the laboratory to check whether the composition was constant. Interpretation: If all the water parameters remained constant, the pumping was of a single type of water. This implies (1) the pumping test interpretation can be done in a straightforward


Chapter 18

routine and (2) the water quality can be predicted to stay constant at recommended pumping rates. Water properties change during the pumping test. In such cases all the samples have to be sent to the laboratory for analyses in order to determine the pattern of change (continuous, abrupt, after how much pumping, which end members are involved). Interpretation: At least one water type encroached and its properties may be assessed. A hydraulic interconnection between the two water bodies is established, being of a leaky natureoperating whenever the pressure required for movement is appropriate. Two practical conclusions can be reached: (1) the new information has to be taken into account in the interpretation of the pumping test data in terms of transmissivity and recommended safe yields, and (2) if the mixed water quality is adequate, the recommended pumping rates may be relatively high (as deduced from the pumping test). However, if the water quality deteriorated, pumping should be limited, and water quality checked often.

Water table change in adjacent wells is of highest interest, as it reveals existing hydraulic interconnections. Hence, every pumping test has to be prepared for water table observations in as many neighboring wells as possible. Pumping of adjacent operating wells may better be stopped, and the pumping test should be done only after the water table in all the other wells has stabilized. Depth of the dynamic water table in the pumped well should be continuously monitored as well. Presentation of pumping test data may include graphs of water table change in the pumped well, as well as in the observed neighboring wells. For the pumped well all other parameters, e.g., temperature, salinity, and concentration of the different ions and isotopes, are best plotted as a function of pumping. The last can be presented as a function of pumping time, pumping rates, and/or cumulative discharge.

18.2.6 Specications
Specications of the routine measurements at the monitoring network should be . . Clearly specied, including occasional specic measurements at selected stations. As simple as possible to perform in the eld, and so should be the sample collection procedure.

Water Quality, Monitoring, Education


. . . .

Minimal, in accordance with nancial limitations, but enough to secure warning in case of adjacent sources of potential pollution, or water supply management failures. Performed with calibrated and well functioning instruments, and samples should be collected according to procedures required by the analyzing laboratories. Samples have to be well kept and rapidly transferred to the laboratories. Field measurement data and laboratory results have to be rapidly transferred to the data bank.

18.3 Active and Efcient Data BanksThe Structure and the Challenges
There are data banks that collect data but very little is done with the information. In a cynical mode, let us make sure that our data bank will not be a data sink.

18.3.1 Data Bank Challenges

Groundwater research and monitoring produce large amounts of data of many kinds. These data have to be gathered at one placethe data bank. Sources of data are the drilling reports, results of the monitoring network, scientic research publications, and data stored by various organizations. Data banks are essential, but they are justied only if they are active and user-friendly. Staff have to put the information into use, for example, in the following modes: . . . . Storing the data in a user-friendly and accessible way so that researchers, planners, management personnel, and other customers can readily retrieve the data they need. The data have to be stored in a form that is easy to understand and use (e.g., in the form of tables, maps, transacts, depth proles, ngerprint diagrams, composition diagrams, etc.). The data bank personnel has to disseminate the information through periodic and special reports, maps, and other graphical representations. Data banks can issue alarms in real time to management personnel and decisionmakers.


Chapter 18

18.3.2 The Monitoring Network Reference Book

Once the thorough investigations of the networks stations have been completed (section 18.2.4) and the routine measurements have been specied, the data should be put together into the networks reference book. The book is essential for the optimal operation of the monitoring and for the best interpretation of data by a wide ciricle of potential users. The book should include: . . The results of the land use and potential pollutants survey (section 18.2.2) A concise description of each station, including (1) name and location, (2) the data obtained in the thorough investigation (section 18.2.4), (3) data from other organizations and professional literature, (4) the considerations that lead to the inclusion of each station in the network, (5) the recommended routine measurements Geologicalhydrological cross-sections (Fig. 18.2)

The network reference book may be prepared to a high standard, with color maps and diagrams.

18.3.3 Regional Data Compilation

There is often a gap between the scientic and management value of data, accumulated by different agencies, and the real use of the data. A common situation may be described by a mountain of data growing in front of personnel that are too busy to approach it. Hence the need of data compilation that will . . . . Provide an overlook Be useful to understand the water systems Be helpful to scientists, modelers, decisionmakers, and project managers Be provided in real time

First the study areas or regions for which regional compilations will be prepared will have to be dened. These may be drainage basins, geohydrological structures, mapping sheets, administrative regions, or other modes of classication. At the second stage the order in which the regional compilations will be prepared has to be determined. There are many ways of data processing; a few examples are . . River cross-sections and composition diagrams Time series diagrams of selected water sources

Water Quality, Monitoring, Education


. .

Depth proles of selected wells (section 7.3) Composition diagrams looking for possible mixing of different groundwaters (section 6.6) and identifying water groups (Fig. 6.16)

The preparation of the data compilations may well be a joint product of the data bank personnel and external experts.

18.4 Water-Related Education Activities

Water is a resource that is vital to everyone. And water is a vulnerable asset that can be deteriorated by man. These points together make it clear that the fate of the water resource is of interest to every person. We, the scientists and personnel involved in water research and exploitation, have access to the observations and data and are familiar with the problems of water supply and its sustainable management. So we have the mission of sharing this information with the public, having the following goals in mind: . . . To contribute to the general knowledge To raise the awareness of the need to protect water To point out how water can be saved and protectedby everybody as individuals and as voters that can encourage the decisionmakers to act positively

The recommended strategy for the educational mission is From observations and understanding to appreciation of the resource and its conservation.

18.4.1 Key Topics for Museums, Exhibitions, and Teaching Activities

Let us discuss the education aspect of the global water cycle in two steps: rst the extended list of potential topics, and then how these topics can be integrated into water and man science museums (section 18.4.2), local exhibitions (section 18.4.3), teaching at schools (section 18.4.4), and teaching at universities (section 14.4.5). The topics are by and large elucidated in the present book. List of key topics of the global water cycle. . Waterthe unique uid


Chapter 18

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Waterthe magic liquid of our planet The special properties of waterthe related physics and chemistry The global water cycle

Measuring and studying water There are groundwaters of all kinds Information encoded into water during its cycle (section 1.3) Water taste and smell (section 8.2) What is dissolved in natural waterthe chemical compounds (section 1.2 and Chapter 6) Temperature and other physical parameters (sections 4.7 and 8.3) Soap as a means to identify hard water Simple kits to analyze water What is the isotopic composition of water telling us? (sections 5.2 and 9.3) How do we know that some groundwaters were buried thousands of meters? How old is groundwater? (sections 10.4, 11.4, 14.5, and 14.11) Water data banks and monitoring networks

Man and water The history of man exploiting water (section 17.2) The incredible diversity of our uses of water Water steam and the Industrial Revolution Man polluting the water resource (Chapter 16)

Fostering the water resource We can cut substantially our water consumption Treated waters Desalination Decreasing the use of detergents to protect groundwater Wise irrigation (section 17.5.3) Landlls threaten groundwaterminimizing wet household garbage Planned street runoff inltration Using roof water Mineral (bottled) water Drinking water standardslearning the different parameter groups (section 18.1)

Water Quality, Monitoring, Education


. . . . . . . . . . . . . . . . . . . .

The need for nationwide clean management (section 17.3)

Water supply How does water reach our tap? Surface water reservoirs Groundwater pumping Deep fossil groundwater as a strategic reserve

Water and the geological dynamics The world of karstic features (section 2.9) Erosion is driven by water internal terrestrial energy sun energy How bizarre would our landscape be if water did not exist! Since when has water been on Earth? The drying up of the Mediterranean Sea 6 million years ago

Ocean and fresh continental water interdynamics How saline is ocean water? How saline is rain and snow water? Rivers are more saline than rain waterthe sea spray phenomenon The salt cycle is operated by the water cycle Seawater encroachment (sections 6.11.1 and 17.6.1) Key role of the oceans in the dynamics of the global water cycle The sea has invaded the continents and retreated countless times

The active water cycle (Chapter 2) . . . . . . . . Runoff travels down the landscape to the base of drainage the sea surface The through-ow zone (sections 2.12.5 and 2.13) Groundwater ow is by gravity (section 2.8) Beneath sealevel groundwater is static and fossil Renewed and nonrenewed groundwater resources Rockstheir hydrological properties (sections 3.13.4) Aquifers and aquicludes (experimenting) (sections 2.3 and 2.7) Anatomy of springs

Glacierspast and present . Polar ice caps


Chapter 18

. . . .

Icebergs and oceans The ice ages and glacial sediments Deciphering paleoenvironment information encoded in polar ice

Looking at the water contained in rocks beneath the oceans . . . Interstitial water of seawater origin Connate water entrapped in rock-compartments (section 2.14) Drying up of the Mediterranean Sea, recorded in the underlying water

Static fossil groundwater . . . . Static water entrapped in rock-compartments Identifying fossil groundwater Diversity of water types in sedimentary basins Formation water: continental meteoric and tagged by brinespray

Thermal waters . . . . How is groundwater heated? (Fig. 4.18) Spas and water parks Boiling and superheated groundwaters Geysers and fumaroles

Biological evolution was propelled by the global water cycle . . Changing ecological environments are a prerequisite for plant and animal new mutations to thrive (quoting Darwin) The continuous change between continents exposed to fresh water and oceans covered by saline seawater as an example of the geological dynamics that propelled biological evolution

18.4.2 Water and Man Science Museums

Such institutions are a must in major cities, and it will be most interesting to see how diverse they can be. The wide topic of the global water cycle and the close relation of man to water provide a master outline for a specic type of geological science museum. These museums have the following aims: . . To contribute to the general knowledge of the public To elucidate the fascinating story of terrestrial water, which is largely unknown to the public

Water Quality, Monitoring, Education


. . .

To demonstrate how different elds of science can be focused and implemented on a common subject, in this case water To familiarize visitors with water as a resource To build appreciation of water and provide the know-how needed to protect it

Some principles to be followed include . . . . . . . To transfer of knowledge along the approach of applied science, namely, from observations and measurements (i.e., facts) to logical conclusions To conduct dialogs with visitors who will have opportunities to provide valuable feedback To use case studies to illuminate concrete observations, problems, and solutions To have simple experimental hands-on displays To address all ages and levels of knowledge To have an active information desk, supported by a library of short lms and information sheets to provide answers to questions raised by visitors To provide, where possible, an outdoor exhibition with large water-related natural features and equipment elements

Topics presented by the facility may include the following: . . . The list of topics presented in section 18.4.1 covers 13 main subjects, each of which encompasses many subtopics that all together will easily ll up a full-sized museum. Within each group of topics there is plenty of room for the selection of the items and issues that will be exhibited with regard to particular examples and case studies. Exposure to activities of water-related volunteering organizations is also encouraged.

18.4.3 Local Water-Related Exhibitions

These can be a valuable entity of every city and each town. These exhibitions are small compared to a full-sized museum, the length of an average visit being around one hour. Selected topics from the extended list in section 18.4.1 can be highlighted in connection with local assets of nature or local human achievements. Emphasis in this case will be on the local features those that every inhabitant and each visitor can see and sense. The aims of such exhibitions include:


Chapter 18

. . . . . . . .

To draw attention to local natural water-related assets To contribute to local consciousness and local pride To encourage local excursions and draw attention to points of interest To foster awareness of water-related issues To convince visitors to respect the water resource and protect it

Some principles guiding such exhibitions are: To have a dynamic exhibition at which displays are frequently changed and constantly updated so that repeat visits become a habit To use local case studies and local problems to explain topics selected from the types presented in section 18.4.1 To describe and explain self-guided tours in the surroundings that expose water-related natural features or functioning installations

Topics that may be addressed by local exhibitions include an assortment of the topics listed in section 18.4.1, emphasizing information on local assets (e.g., springs, rivers, karstic features, lakes, wetlands, waterfalls, sea shores, wells, sections of the water monitoring network, spas, hot springs or wells, ancient bath houses, water mills, ancient and modern irrigation systems, water towers, dammed water reservoirs, well elds, water treatment stations, snow-related features). For each of the local assets there is high interest in providing geological and hydrological cross-sections, the chemical and isotopic compositions, and what they tell us. What is the age of the water in these cases? Are there any pollution problems? Information of what has been done for these water resources and what was successful should be provided. Visitors will also be interested in access to the relevant water data bank.

18.4.4 Teaching at the Schools

At the kindergarten and primary school class level the active water cycle is a suitable topic, along with simple measures by which we can save water. In middle school classes the man and water topic may be developed and visits to neighboring natural water assets as well as coverage of the water supply issues are appropriate. At the high school level the global water cycle can be tackled, and mini research projects are suitable. A list of examples may be drawn from section 18.4.1. Use of local case studies is only natural, and connection to the water data banks is most welcome.

Water Quality, Monitoring, Education


The above-mentioned topics may be taught as part of various science courses. At the upper levels there is room for a full water-related course to be based on selected topics from the list given in section 18.4.1.

18.4.5 Teaching at the Universities

A basic course on the topic of water and man or a similar subject is due as part of the introductory courses offered at colleges and universities. There are several aims: . . . To familiarize students with the unique terrestrial uid and the global water cycle To expose students to the research methodology of observations and measurements that lead to conclusions that provide the basis of our understanding of the studied natural systems To encourage students to be actively interested in the water-related issues that are on the decision makers agenda

A graduate level course (one or two semesters), based on the present book, is also warranted. Such a course suits students of the following professions: hydrologists, hydrochemists, geologists, geomorphologists, petroleum experts, water-based recreation and therapeutic experts, ecologists, environmental scientists, urban and statewide water supply operators, and pollution control managers. Field trips to relevant assets of nature and management installations are a must. Mini research projects on worldwide problems or local issues are most welcome. Acquaintance with monitoring networks and data banks is an intrinsic part of such a graduate water course.

18.5 Summary Exercises

Exercise 18.1: You are going to give a lecture to high school students about drinking water standards. What are the three main points you will address? Exercise 18.2: Which groups of compounds are addressed by the drinking water standards? Exercise 18.3: A well is planned to monitor whether pollution from a factory is reaching the local unconned groundwater. Is there a preferred direction to site the well? Exercise 18.4: By what logic have the surface water monitoring stations been placed in the terrain shown in Fig. 18.1?


Chapter 18

Exercise 18.5: In Fig. 18.1 a sewage treatment plant is marked. Is it well monitored? Exercise 18.6: Which considerations do you think lead to the location of the two geologicalhydrological cross-section lines shown in Fig. 18.2? Exercise 18.7: Have a look at the case study reported in section 16.3.3 and Fig. 16.3; can you see how it can be used for a museum item or school topic? Exercise 18.8: Go over the case study discussed in section 16.3.8. For which educational activity does it t?


19.1 Why Reports?

Scientic research has to be summed up in a written format with appropriate circulation. The nal stage of any research is a report, needed to Expose the work to critical comments by other specialists Convey the ndings to the authorities that nanced the investigation Convey the results and recommendations to the engineers and other researchers who have to execute the recommendations Document the ndings for future investigators Share your experience with the international scientic community In addition to the listed reasons for preparing written reports there is a benet in report writing that cannot be overestimated: the preparation of the report clears the researchers mind, clears up inconsistencies, and focuses thoughts on the essential issues. Thus, preparing reports is an integral part of the scientic thinking process.

19.2 Types of Reports

Written reports vary in length from a single page to hundreds of pages. The length of a report depends on the type of report and the specic nature of each study. A research proposal is, in most cases, the rst document to be written in any investigation. It should focus on the problem to be addressed, work done so far, strategy of the investigation, suggested schedule, organizations


Chapter 19

involved, and required budget. A research proposal should be brief and contain only the most important points. Progress reports are required periodically by the nancing agencies. Beyond that they are also of prime importance to the researcher. Progress reports force the researcher to realize that data have to be processed and discussed continuously. Conclusions reached in progress reports inuence the continuation of the study as priorities are reassessed. Progress reports have to contain substanceresults and preliminary discussion of the data. The length of a progress report is basically dened by the amount of data and the maturity of their processing. Final reports are just thatnal. In other words, they should contain all relevant information and be comprehensive. Final reports are the longest of all report types and may contain hundreds of pages. Final reports may have an outline similar to scientic papers, but they are supported by all the raw data, mostly organized in appendices. Because of their length, nal reports should contain an abstract. Scientic papers are often an outcome of a nal report. A scientic paper should be concise, a task that can be achieved by referring to the nal report for details. A scientic paper should deal with a local problem, but in a mode that is applicable elsewhere. Thus scientic papers have a methodological aspect that is of much importance. In optimal cases the specic study serves as a case study to demonstrate the methodology of the scientic approach. No recipes exist for writing reportseach case has to be solved for itself. The following sections deal with the various parts of a report in a generalized form.

19.3 Internal Structure of Reports 19.3.1 Name or Title

The name of a project is, in a way, a one-sentence summary of the most essential parts of the whole study. Thought has to be given to proper formulation of the name of the project, the report, or the scientic paper. This is best done by rst listing the key words that should be included: . . The main issue e.g. pollution, recharge or discharge estimates, mixing of water types, groundwater dating, pumping consequences, general survey Methods used e.g. pumping tests; chemical analyses and isotopic analyses; dating by tritium, 14C, 36Cl, or 4He; trace elements; specic polluting compounds analyzed; monitoring; water table data, temperature surveys

Hydrochemists Reports


. . . . . . .

Geographical location of the study

Below are examples of report titles, based on selected key words: Chemical and isotopic survey of springs and wells in the Paradise Valley Flow direction in the Apollo aquifer, Utopialand, traced by a landll leachate Leakage of the Fantasia Dam, traced by environmental water isotopes A groundwater transect through the Episode Valley: hydrological, chemical, and isotopic parameters Identication of recharge areas of the Maximum Springs, applying stable isotopes, tritium, carbon-14, and helium Paper factory as a possible source of salinization of the Alpha aquifer, Betaland

19.3.2 Abstract
The abstract provides a brief summary of the major outcome of the research. It does not deal with the history of the project, the type of measurements conducted, or hypothesis that could not be conrmed. The abstract should avoid noninformative sentences. For example, what is wrong with the following abstract: An intensive study has been conducted on a large number of water sources in the study area. The paper deals with the various aspects of the main problems, leading to a series of practical recommendations. This example contains no single item of information, and the abstract gives the reader no idea of what the paper is about. Noninformative words are a large number (instead of 21 wells); water sources (instead of a lake and 12 springs); study area (instead of Wisdom Valley, Bestland); the paper deals with (should be omitted); various aspects (instead of consequences of clearing of the Green Forest); leading to a series of (should be omitted); practical recommendations (instead of limiting forest clearing to no more than 10% of the area is recommended). The abstract should contain the most important data, for example, The Curiosity aquifer is saline (15002200 mgTDI/1), Na-HCO3 dominated, with temperatures of 59 + 28 C, devoid of tritium, 14C concentrations of 68 pmc, ddD of 120 + 10% and d1 8O of 16 + 2%. Recharge from the Top Mountains is concluded, depth of circulation being > 850 m, effective age is 22,000 + 3000 years.


Chapter 19

So far no invasion of the Filthy Landll leachate has been noticed, based on the chemical and biological data.

19.3.3 Targets of the Study

Hydrochemical studies may be motivated by pure scientic curiosity, urgent management problems, or routine surveys. Behind each of these motivations stands one or several targets and they should be spelled out. There is a saying that a good question is half its answer. By the same token it may be said that well-dened targets promise well-conducted research and a focus on the major issues. Which of the following phrases are well-dened hydrochemical research targets? . . . Checking hydraulic interconnections between the Grand Dam and the Greytown municipal well elds I and IV Conducting general observations on the local hydrological system Testing the applicability of 14C dating techniques to the noncarbonate aquifers of the Glorious groups in the Papaland

The rst and last examples are well-dened hydrochemical research targets because they are specic and focused.

19.3.4 Denition of the Study Area

Terms like the northern Great Artesian Basin, surroundings of London, or arid zones of Israel may be suitable for the name or title of a project, but in the report or the paper itself the study area should be precisely dened. The aerial denition may be by coordinates or by names of geographical boundary objects. The study area should always be dened on a clearly readable map, along with a map that shows the study area in a larger geographical frame, for example, a country.

19.3.5 Hydrological Inventory

The report should have at its beginning a section describing the hydrological inventory of the study area: seacoast, lakes, marshes, rivers, dry riverbeds, springs, abandoned wells, operating wells, observation boreholes. Sources of available information on these water bodies should be discussed, such as published papers, reports issued by various authorities, research theses submitted at universities, and data stored in archives. The exact titles can be included in the reference list of the report. To each source of information a sentence or two should be added on the nature and extent of the included information, such as water level measurements, discharge values, periodic

Hydrochemists Reports


quality checks, borehole and casing data, and chemical and isotopic analyses.

19.3.6 Human Activities and Installations Relevant to the Study

A clear and concise description should be provided on relevant human activities in the study area. These should include dams, drainage channels, recharge installations, sewage ponds, industrial efuent ponds, uid waste disposal installations, pumped well elds, and the nature and extent of agricultural activity, including irrigation schemes and the use of fertilizers (types, quantities) and pesticides (types, quantities). Part of the information may be abstracted from detailed maps, but most information has to be obtained directly from local authorities, farmers, and industry.

19.3.7 Strategy of the Investigation

A good investigation is not done by shooting in all directions. It is performed with an outlined strategy. A clear distinction has to be made between knowns and unknowns, and between established methods that have already been tested and calibrated versus developing methods that have to be checked and calibrated. Formulation of a preliminary conceptual model based on existing data is most helpful in dening the strategy of an investigation. Such a preliminary conceptual model should include alternative recharge areas, modes of ow, ow paths, mixing combinations, sources of heat, dissolved solids and dissolved gases, and alternative routes of potential contamination. In the second stage, criteria should be dened by which incorrect alternatives can be ruled out and correct alternatives can be proven. In the third stage the research strategy is formulated, focusing efforts on necessary observations and collection of required data. The following is an example of an investigation strategy, taken from the introduction of a paper on research of CO2-rich springs: The strategy of data processing was (a) searching for water groups of common chemical composition, (b) searching for geological or geographic logic of the established chemical groups, turning them into geochemical water groups, (c) in each group the distribution pattern of ion concentration variations was studied. Mixing lines emerged, and the properties of the end members were qualitatively dened, (d) once it was found that HCO3 is the dominant anion, accompanied by different cations, possible waterrock interactions were explored to explain the identied geochemical water groups,


Chapter 19

(e) the stable hydrogen and oxygen data were processed to look for the role of local recharge (lying on the meteoric line) versus waters with modied isotopic compositions (e.g., 18O shifts). For water lying on the meteoric line the average recharge altitude was calculated from the isotopic composition, (f) the tritium data were interpreted in terms of pre and postnuclear bomb test water components, (g) the temperature data were interpreted in terms of depth of circulation of the groundwater end members, (h) d13 C values, obtained for the CO2 emanating in a few mofettes, and bubbling in a few springs, were applied to dene constraints on the possible origin, i.e., decomposition of organic material, heatinduced decomposition of carbonatic rocks, or mantle contribution. This choice of CO2 origins was narrowed by noble gas data: nonatmospheric He is observed in the springs, explained as accompanying the ascending CO2. 3He/4He ratios of 0.1 of the atmospheric ratio ruled out a mantle origin, leaving both the He and CO2 as of crustal origin.

19.3.8 Results
Data are the major product of every investigation. Our interpretations, conceptual models, and recommendations may all be challenged by other investigators, or turn out to be wrong by our own subsequent work. Observations and measurement results, however, may always be incorporated in new models and coupled with additional observations. Hence, results are a most important part of a report or paper. Results should be presented in a way that makes them usable by other investigators. Data are best presented in well-organized tables (section 6.1), along with relevant technical data, such as who measured each parameter, measuring error, limit of detection, resolution, results of duplicate and triplicate measurements, and measuring methods applied. A major part of data tables may be included in the appendices of a report.

19.3.9 Data Processing and Interpretation

Hydrochemical data can be processed in a variety of ways and, accordingly, can be presented in many different ways, including ngerprint diagrams (section 6.2), composition diagrams (section 6.3), histograms, maps, transects (section 7.9), and a host of other graphic modes. Presentation of processed data is closely linked to interpretation since the obtained patterns reect distinct boundary conditions, such as the number of water types occurring, mixing of water types and mixing

Hydrochemists Reports


percentages (natural and polluted systems), hydraulic interconnection and hydraulic isolation, positive and negative correlations between parameters, and directional changes in properties (on transects and maps) indicating directions of ow and modes of intermixing. Much thought should be devoted to determining the best way to present processed data in a report. The order should be dened by the study strategy and the logic of the case presentation. In a poorly organized report, use is often made of statements such as this point is discussed later on or the relevant data are presented in a later section. In a well-organized report topics are discussed in a progressive order. The data processing and interpretation sections of a report lead each to a subconclusion or dene a constraint, all to be taken into account in the formulation of the overall conceptual model.

19.3.10 Exact Terms, Logic, and Informative Statements

Conclusions, boundary conditions, and conceptual models have to be formulated with the aid of exact and relevant terms. . What is wrong in the following statement? The shallow wells contain fresh water and therefore contain postbomb tritium. The term fresh water relates to low TDI concentrations, whereas post-bomb tritium relates to a recent age. The presence of post-bomb tritium indicated the water is of a recent age, and not vice versa. What is wrong in the following sentence? The low temperature of the springs indicates dominance of a recent water component. Low temperature may indicate dominance of a cold water end member, but temperature does not relate to age. What is wrong in the following phrase? The water is old, as indicated by its high salinity. High salinity may be caused by many processes (evaporation, intermixing with saline water, dissolution from rocks) and is not an indication of a high groundwater age.

Logic has to be maintained in every sentence of a report. Cause and outcome should not be mixed, neither should observation and hypothesis. . Correct the following statement: The new deep wells tap mixed waters and therefore have


Chapter 19

discordant ages. Observation (discordant ages) leads to the conclusion (the water in the wells is a mixture) and not vice versa. Correct the following statement: Piston ow is assumed to dominate in the Good Hope wells that have seasonally varying temperatures. The order should be reversed: observation (seasonally varying temperatures) leads to the conclusion (dominance of piston ow). The term assumed is out of place.

Statements in a report should always be informative as much as possible. Examples: . How can the following sentence be made informative? Group A waters are warm and group B waters are cold. Warm and cold are relative terms, but providing the relevant temperatures will make the sentence informative: Group A waters are warm (5264 8C) and group B waters are cold (1517 8C). Is the following sentence good enough to be included in a hydrochemists report? Magnesium is correlated to bicarbonate in two out of the three water types prevailing in the area. This sentence should read something like: Magnesium reveals a linear positive correlation in water groups I and III of the Grand Scheme project area.

19.3.11 Conceptual Model

Conceptual models (section 1.5) should be presented in a clear, logical, and concise way. Each part of the model should be based on a specic subconclusion or constraint, reached in previous parts of the report. A conceptual model should discuss alternatives and explain criteria used to select the preferred possibility. A conceptual model should, as much as possible, be formulated in terms that will lead to conclusions and recommendations. Therefore, discussion of a conceptual model should also include denition of weak points and open possibilities. The conceptual model is, in a way, the heart of every investigation, and much thought should be devoted to its construction and proper presentation.

Hydrochemists Reports


19.3.12 Quantitative (or Mathematical) Model

Parts of a conceptual model, or all of it, may in many cases be quantied, using mass or energy balances, chemical equilibria and degree of saturation calculations, ow velocities calculated by hydraulic parameters, or velocities calculated via isotopic age indicators. In presenting the mathematical calculations, knowns and unknowns have to be clearly dened, and basic assumptions have to be discussed. Each calculation should be accompanied by an evaluation of its degree of condence.

19.3.13 Scientic Conclusions

Models may be followed by a discussion of the scientic conclusions reached in the study; for example, which elements and compounds tend to behave as conservative parameters; which ions participate in secondary waterrock interactions; or reliability of isotopically based calculations, such as recharge altitude (section 9.8) or d13C values as a tool to correct observed 14 C values for waterrock interaction. Scientic conclusions are of a local nature but of a general value, because they can be applied to studies in other regions as well.

19.3.14 Operational Recommendations

Operational recommendations can be of a practical aspect, for example, rate of suggested pumping or the spacing of new wells and their required depths. Operational recommendations can also relate to further research needed, for example, new parameters to be measured, special pumping tests, or new wells. Recommendations have to be clear, and their reasoning should be explained. Does the following recommendation t the described specications? A few deeper wells should be drilled to get a better understanding of the system. This recommendation is totally worthless: A fewhow many? What are the technical specications? Where? To get better understandinghow? By closing large gaps between existing wells? By better installation of the wells? By proper pumping tests? Recommendations for further research should be given only if they are fully justied. Vague words such as deeper, more, or better should be replaced by explicit denitions. Recommendations should also be weighed in light of the costs involved.


Answer 1.1: It seems easy to grasp that along the seacoast all rivers ow into the sea. The observation that all rivers run into the sea describes runoff. Water ows down along the topographic relief, and the sea is the terminal base of drainage. Answer 1.2: The law of mass conservation. When we pour water into a vessel, the level of the water risesnot so in the case of the sea. So, there must be an outlet of water from the ocean. Answer 1.3: Two segments of the water cycle were concealed: the evaporation of water from the ocean, forming clouds that transport water into the continents, and the ow of water underground. Answer 1.4: Once the water (runoff or underground drainage) is returned to the sea. There all water is well mixed and the accumulated information is wiped out. Answer 1.5: The temperature that prevailed at the base of the aerated zone at the time of recharge (via the concentration of the atmospheric noble gases); the depth of circulation or storage (via the water temperature); the types of rocks passed (via the chemical composition); the time the water stayed underground, i.e., its age (via the decay of tritium and 14C and the accumulation of radiogenic 4He and 40Argon). Answer 1.6: Erosion that changed the Earths face continuously.


Answers to Exercise Questions


Answer 1.7: Marine fossils that go back over a half billion years and similar sedimentary rocks that are signicantly older. Answer 2.1: 1C; 2F; 3B; 4D; 5E; 6A.

Answer 2.2: Every well has to be dug out or drilled (rock and soil material has to be taken out). Water exists underground only as a uid stored in rock voids (pores, ssures, and small cavities). The well space acts as a collecting tube for the water in the rocksthe rocks are yielding water to the well. Answer 2.3: In an extra-rainy year inltrating rain is pushed beneath the depth of evapotranspiration activity, and a signicantly large portion ows into the saturated zone and is turned into recharge. In contrast, in an extradry year water inltrates to a shallow depth (about the root zone), and all of it is returned to the atmosphere by evapotranspiration. Answer 2.4: To assess recharge we also need the range of annual precipitation intensities or the variance. There are reports of recharge in arid areas that is sustained by once-in-a-decade heavy rain events. This is an example of the problems that are connected with the selection of single representative parametric valuesthey cannot adequately describe an entire system. Answer 2.5: The rst water occurrence indicates the existence of a phreatic aquifer, and the second occurrence of water may indicate the existence of an underlying conned aquifer. However, the drillers could have difculties in telling water occurrences apart if the drilling itself is conducted with water. Additional data are always neededwater table, water temperature, and water chemistry. Differences between the properties of the deeper and shallower waters will establish that two separated aquifers exist and that the deeper one is conned. Answer 2.6: The spring has a temperature of 15 8C, whereas the local average annual temperature is 19 8C. Thus the spring water remembers the low snowmelt temperature. Due to the rapid ow in karstic conduits, temperature equilibration is incomplete. In addition, the discharge varies signicantly during the year in high correlation to the snowmelt season. Answer 2.7: The time that elapsed since the water was recharged into the saturated zone. Water that is recharged into an unconned system at its inland reaches attains a relatively high age by the time it arrives at the base of drainage at the sea, but along its ow path it gets mixed with local recharge that is younger. Hence, in a phreatic aquifer, water age does not have a singular value (the average age will be on the order of a few


Answers to Exercise Questions

decades). In trapped aquifers, the age will indicate the time that elapsed since the system was isolated from active recharge. This will be a singular age, and of much interest concerning the paleohydrology of the study area. Answer 3.1: High-quality drinking water is low in dissolved solids, less than 800 mg/l. Answer 3.2: 2A, D, G; 3A, D, G; 4A, D, F; 5C, E, H; 6 occasionally A, occasionally C; occasionally D, occasionally E, G; 7C, H; 8B, D, F; 9B, D, F. Answer 3.3: Lithology, fractures and open ssures, dissolution cavities, rock cementation, layering of rocks, occurrence of intrusive bodies, and the nature of faults and folded structures. Answer 3.4: Similar chemical and isotopic compositions of the waters of wells I and II support the hypothesis that these wells are hydraulically interconnected. Differences in the water properties of wells III and IV support the hypothesis that these wells are hydraulically separated. Answer 3.5: Answer 4.1: Atmospheric (section 3.7.1). The answer is given in Fig. 4.1.

Answer 4.2: masl stands for meters above sea level (section 4.1). The altitude of the water table was 553 masl (see also Fig. 4.3). Answer 4.3: The arrows in Fig. 4.4 show the direction of ow along the steepest gradient. However, some ow goes also from the area of the well with a 153 masl water table to the area of the well with a 137 masl water level and so on. These side ows are slower because they occur along smaller gradients (compare to the structure of the equation of Darcys law, section 2.10). Answer 4.4: The fault in Fig. 4.6 was plotted on the basis of abrupt changes in recorded lithologies between wells 6 and 7 (Table, Fig. 4.6a). An alternative interpretation: The calcareous sandstone was deposited on a limestone relief with a steep paleo-erosional face between the locations of wells 6 and 7. Answer 4.5: The water table curve in Fig. 4.8 is not correlated to the precipitation record (no match of peaks). The reason: the well is recharged by various sources not included in the precipitation recordrecharge is by the time of snowmelt and not by the time of snow fall. In addition, water demands are not reected in the precipitation record. In other cases the

Answers to Exercise Questions


water tableprecipitation record correlation may be good, indicating a different hydrological history. Answer 4.6: The river water ows to the wells mainly via conduits or zones of preferred water transmission. Answer 4.7: Because the hydraulic gradient is zero (the two wells plot on the same water table contour). Answer 4.8: Locally, water from aquifer I could leak into aquifer II, provided the pressure in aquifer II was signicantly lower than the pressure in aquifer I. Answer 4.9: Provided two aquifers (e.g., one below the other) have the same temperature, breaching during the pumping test would not be noticed on the temperaturedischarge curve. So what may be recommended? Answer 4.10: (1) In October 1960 the temperature of the river was 64 8F and that of the closest wells was 50 8F (the wells were colder); (2) in January 1961 the river was 32 8F and the closest wells were 60 8F (the wells were warmer); (3) in March 1961 the river was 41 8F and the closest wells were 45 8F (the wells were slightly warmer); (4) in September 1961 the river was 77 8F and the closest wells were 50 8F (the wells were colder). Thus the temperature of the wells followed the temperature of the river, but with a time lag indicating the river recharged the wells. Answer 4.11: The contours in Fig. 4.22 depict the annual change of groundwater as measured in wells. Generally, the values drop as the distance from the river increases (from > 30 8F near the river to < 10 8F a few hundred meters away). Two explanations come to mind: (1) recharge to the wells decreases with distance and, hence, the temperature is closer to the local average annual ambient temperature, or (2) the distant wells are discharged as well but the water travels a longer time, allowing for temperature equilibration with the aquifer rocks. The authors prefer the rst explanation. This shows that additional data are needed; can you give an example? Answer 4.12: The changes over the measured period were small (only 1.5 8C, from 120 to 167 l/min, and from 523 to 578 ms/cm. The question whether these temperature, discharge, and conductivity variations are signicant is answered by comparison of the changes to the accuracy of the measurements. In the discussed case measurements were done to + 0.2 8C, + 5 l/min, and + 15 ms/cm. Thus the observed changes were of signicance.


Answers to Exercise Questions

This shows that the accuracy of the data has to be indicated in each case (sections 5.75.10). Answer 5.1: Answer 5.2: G. 24.3; 2 ; (24.3:2)/1000 12.1 mg/l. 1C; 2F; 3B; 4H; 5A; 6J; 7D; 8E; 9I; 10

Answer 5.3: Milliequivalent per liter. It is used to describe the concentration of ions dissolved in water. An equivalent is the number of grams that equal the respective ionic weight divided by the valency. 35.5 mg/l. Answer 5.4: The sum of cations equals the sum of anions in this (synthetic) case. Hence the reaction error is 0 meq/l, or 0%. Answer 5.5: The reproducibility is a measure of how well a measurement can be repeated. The mean value of the given measurements is 12.0 8C, the mean deviation is 0.1, hence the reproducibility is + 0.1 8C, or + 0.8%. Answer 5.6: (a) A quick glance reveals that the value of 202.02 mg/l is outstanding and most probably results from a typing error and should be 102.02 mg/l (it was checked and admitted by the laboratory); (b) if the resolution is 2 mg/l, there is no reason for the laboratory to report the data with two decimal places. The data should be reported as 101, 99, 97, 103, and 102 mg/l; (c) the average value is 100 + 2 mg/l (an analytical error of 2%), which in most cases is acceptable. Answer 6.1: This limited set of data provided the researchers with the preliminary conclusion that the wells abstracted water from at least two aquifers of different chlorine concentration, and that the produced mixing ratio varied according to pumping intensity and/or alternations of rainy and dry seasons. Thus all available water sources in the region were included in the study in order to detect the intermixing groundwaters. Later research revealed that the wells tapped up to three aquifers: the Kalahari sand (hosting fresh recently recharged water), underlain by basalt (hosting saline water), and beneath the Cave sandstone aquifer (hosting fossil slightly saline groundwater) (Mazor et al., 1977). Answer 6.2: Lines extrapolating to the zero points are observed for Li, Na, and K, plotted as a function of Cl. The temperature is roughly positively correlated to the concentration of these ions. Thus, if only these parameters were measured, the conclusion could be reached that one deals with a warm (and deep) saline water end member that is diluted by very fresh and shallow (cold) local recharge water. Yet the correlation lines of SO4, Ca, and Mg extrapolate to the vertical axis, indicating that both water end members are

Answers to Exercise Questions


mineralized to different degrees. The correlation lines of HCO3, Ca, and Sr are horizontal, revealing that the intermixing end members have the same concentrations of these ions. Thus the full picture leads to the conclusion that both end members come from aquifers that contain gypsum (contributing the bulk of SO4 and Ca and smaller amounts of Mg that is present in most gypsum rocks), but the two aquifers differ in that the deeper one contains some halite and the shallower one has no halite. Answer 6.3: Such a ngerprint is given in Fig. 1. The lines of the four springs are nearly parallel, suggesting dilution of a slightly saline end member with various amounts of fresh water. Both end members have similar HCO3 concentrations. More of this case study is given in section 11.10. Answer 6.4: The data span from 0.001 meq/l for the lowest value in the table up to 5814 meq/l for the highest value. To accommodate all these data, seven logarithmic cycles are needed. Is your interpretation of the obtained patterns in agreement with the discussion of these data given in section 6.6? Answer 6.5: The Dead Sea values stand out as being much higher than the values of the springs. Dividing these values by 10 made better use of the space in the ngerprint diagram, and the reduction in the number of needed logarithmic cycles resulted in better resolution of the other lines in the diagram. The diagram can be further improved by multiplying the lithium and potassium data by 10; this will cut another logarithmic cycle.

Fig. 1 Answer 6.3.


Answers to Exercise Questions

Answer 6.6: The researcher concluded that pumping of the aquifer caused vertical migration of salty groundwater from a deeper semiartesian aquifer. Plugging the lower parts of the wells in this eld and/or reduced pumping rates may be recommended for proper management of the fresh water aquifer. Answer 6.7: The sum of cations nearly equals the sum of the anions, hence the diagram is in meq/l. The data, except SO4, plot in clusters, revealing the spring had a constant composition (with random analytical errors). Thus the spring is fed by a single homogeneous aquifer. The SO4 data show signicant variations, in contrast to the other ions. Therefore the quality of the SO4 data should be questioned and a new analysis of SO4 will be needed before any conclusions can be drawn based on this ion. Answer 6.8: The wells tap two distinct waters: (1) wells W-A, W-L, and W-K tap relatively fresh water with a composition of Na Mg > Ca4K4Li and HCO3 > Cl > SO4 > Br; (2) wells W-B and W-H tap signicantly more saline water with a composition of Na > Ca > Mg > K4Li and Cl > SO4 > HCO34Br. The wells tap two different aquifers and no intermixing seems to occur. Hence, the casings of the wells seem to be well sealing in their nonslotted sections. Answer 6.9: No, since the increase in cations is balanced by an increase in HCO3, meaning the underlying clay is most probably not being reached and the water quality is still good. Answer 6.10: Evaporites, as well as clay and shale, since these rocks commonly contain some halite and would signicantly raise the chlorine concentration; limestone and dolomite are not plausible since the sodium concentration is rather high and not balanced by chlorine. The aquifer rocks are most probably igneous rocks or their debris. Answer 6.11: Extreme degree of evaporation of surface water and soil water in the dry season, resulting in the concentration of rainborne salts in playas and salinas. During extra-heavy rain events these salts are redissolved and transported by the recharge water into the saturated zone. This process is common in certain arid zones. Answer 6.12: The well clearly struck gypsum, as a dominant rock or hosted in an evaporitic complex. Valuable information was missed by not having collected water samples from shallower depths during drilling. Careful study of the local rock section, and water quality examination in neighboring wells, may result in the recommendation to plug the lower part of the well and try to reach water from shallower, nonevaporitic rocks.

Answers to Exercise Questions


Answer 7.1: The aim was to understand the sources of recharge to the local through-ow system. Hence, an undisturbed well was needed, and the park area provided it. At rst glance the study may seem to have needed only water level measurements, but data concerning all possible recharge and consumption sources were needed as wellsummed up as precipitation in Fig. 4.8, and much more information of that year is provided in the upper part of the gure. Answer 7.2: One has to understand the problems that bother the spa owner in order to plan the study, but in any case the question arises whether the collected samples properly represent the setup? For example, the water has to be collected at the well head or spring, before the temperature changes and the gases escape; water from two wells may be mixed before entering the specic bathing installation; etc. A visit to the location of study and careful sample collection are essential. Answer 7.3: By preference of wells that meet criteria of the following kind: (1) available information on the well depth, construction, lithology and stratigraphy, and initial temperature, water level, and chemistry (avoid pirate wells); (2) records of measurements conducted in the past; (3) spatial representation of maximum potential aquifers; (4) high yields, if possible; (5) coverage of a maximal range of salinity and temperatures. Based on the results of this rst stage of planning, decide whether you will present the data as contour maps or as transects, and select the nal wells accordingly. Answer 7.4: Date of drilling, water horizons encountered as drilling progressed, their temperature and composition, intervals of loss of circulation uids, depth of the well, the lithological and stratigraphic prole, perforation intervals, initial hydraulic head and temperature of the pumped water, rise of the water table after the water was rst encountered by the drillers (indicating connement), and more. This is indispensable information that justies every effort needed to get the drillers reports. Answers 7.5: Experience reveals that the properties of water often change from the rst minute of the pump operation until a steady state is reached sometime later. The explanation is that the pumping operation draws water from the entire water columnfrom the upper part where recharge and contaminants arrive and possibly from several aquifers passed during drilling. The ideal study of a well starts with its monitoring before pumping starts and continuous monitoring thereafter until the properties stabilize. If the properties do not change, this indicates one deals with a single and uniform body of groundwater, whereas if the water properties change it


Answers to Exercise Questions

indicates different water types are pumped and their properties can be deciphered. If such a detailed study has already been performed once, the following work can be conducted on continuously pumped wells, providing well-average parametric values. Answer 7.6: The fewer the available monitoring points, the more detailed and profound has to be their study. For example, the study should cover a very wide list of parameters measured in the laboratory, a well should be proled after a long enough time of no pumping, each well has to be monitored without pumping and during pumping, and a frequent time series should be obtained. Answer 9.1: The d18O values are 6% for freshwater end member and 4.5% for the Dead Sea, hence the difference, 10.5%, equals 100%. The d18O value of Hamei Yesha is 0%, and the contribution of Dead Sea brine in it is 6 06100 57% 10:5 The corresponding dD values are 30% for the fresh water, 0% for the Dead Sea, 13% for Hamei Yesha, and the calculated contribution of Dead Sea brine to the mineral spring is 55%. The values of 57% and 55% are very close, considering the analytical errors and the inaccuracy of reading the data from a graph. Answer 9.2: Answer 9.3: Answer 9.4: effect). (a) 1385 masl; (b) 1404 masl. dD measurements should serve as a good check. Colder climate and/or heavier rains (causing an amount

Answer 9.5: Calibration of the local isotopic altitude effect. Springs or shallow wells located (a) at different altitudes and (b) at the base of small ridges, to be sure they are recharged by local precipitation. One should exclude springs or wells located at faults, deep wells, or thermal watersall of these may have remote recharge and therefore will not represent an identiable recharge altitude. Answer 9.6: They are recharged by partially evaporated water. One can exclude salinization due to complete drying, as in playas or salinas, because in these locations rainwater evaporates completely, the salts accumulate, and extra-strong rain events dissolve the salts and transport them into the

Answers to Exercise Questions


saturated groundwater zone. In the last case, salinity will be elevated, but the dD and d18O values will be relatively light. Answer 9.7: The HCO3 concentration decreases as a function of salinity increase. The deeper waters reect, by their elevated chlorine concentration, that the wells tapped seawater, and this is supported by the lower HCO3 concentrations. Answer 9.8: By plotting the data on linear axes rather than on a semilogarithmic plot. Answer 10.1: The pre-1952 tritium concentration in precipitation was about 5 TU (decayed to less than 2.5 TU in 1965). The available data (Fig. 10.3) indicate values above 100 TU since 1961. Hence, the water was recharged after 1952 and prior to 1961. This is an effective age. Hydrologically it means rapid recharge. Answer 10.2: Pre-1952.

Answer 10.3: The tritium can be used in this case both as an age indicator and as a tracer (0.3 TU reveals a pre-1952 effective age, and therefore no post-1952 water reached it from the sewage pond, which equilibrated to the prevailing atmospheric tritium value. The tritium concentration in the pond could be measured, or assumed from the local tritium curves. Suppose that the pond contained 300 TU, then its contribution to the well could be at most 0:36100 0:1% 300 Answer 10.4: The conventional method is based on the comparison of the measured tritium concentration in the water sample with the recorded tritium concentrations in precipitation, taking the latter as the possible initial concentration in the water. The tritium-3He method is based on the ratio of two parameters directly measured in the water sample: the tritium and 3He concentrations. Answer 11.1: Post-bomb (post-1952).

Answer 11.2: Pre-bomb, but probably quite recent, since 70 pmc is in fact a common initial 14C concentration. An age of a few decades to a few hundred years (but not thousands). Answer 11.3: More than 30,000 years ago (Fig. 11.1).


Answers to Exercise Questions

Answer 11.4: This is a forbidden combination of high tritium and low 14 C, leading to discordant ages: 6 TU indicates a post-1952 age and 6 pmc indicates an age of several tens of thousands years. This is a mixture of post1952 water with very old water (0 TU, * 0 pmc). Answer 11.5: The Parly-Chennons well is tapping a phreatic aquifer with post-1952 water. Answer 11.6: The Migennes well has already been discussed in the text. It is reported to be a conned well, but the tritium-14C combination indicates two water types are pumped in this well as a mixture. This nature is distinct from the comparison of the repeated measurements (10/67 and 7/69). In the last sample the percentage of recent water was greater than in the rst sample. Corrosion and rupturing of the well casing may have deteriorated the well, so it pumps an increasing amount of shallow recent water. However, such a well may cause a short circuit between the two aquifers: due to different hydraulic pressures, water from one aquifer may ow uncontrolled into the other aquifer. Repair of the well may be necessary. Answer 11.7: The Montier-en-Der well is another example of a well reported to be conned, but the June 1969 sample revealed that recent (shallow) water is pumped as well. Answer 11.8: The Issy well pumps very old water. The d13C value, d13C 15%, reveals no dilution of carbon isotopes occurred in the aquifer beyond the initial waterrock interactions. Hence, an initial groundwater 14C of 60 pmc (at least) may be assumed, and the present value of 3.7 pmc indicates four half-lives have passed (reducing the 14C from 60 pmc to 30, 15, 7, and 3.5 pmc respectively). Thus the water has an age of 5.730 6 4 23,000 years. Answer 11.9: Both gures depict tritium in groundwater as a function of C, revealing the fact that groundwater that contains bomb tritium also has high 14C concentrations, indicating that bomb radiocarbon is present as well.

Answer 12.1: About 700,000 years, as read from the radioactive decay curve given in Fig. 12.1. Answer 12.2: The 36Cl concentration, read from Fig. 12.10, is 120 6 107 atoms/l. The initial 36Cl concentration, read from Fig. 12.10 by the technique explained in Fig. 12.4, was 220 6 107 atoms/l. The respective P36 is 120 6 100/220 55%. Thus the age, read from Fig. 12.1, is about 2.9 6 105 years.

Answers to Exercise Questions


Answer 12.3:

Two half-lives. Hence the age is 600,000 years.

Answer 12.4: The water samples underwent different degrees of evapotranspiration prior to their recharge into the groundwater system. This, in turn, indicates that recharge was at different surface cells, typied by different degrees of evapotranspiration. Answer 12.5: Bromineto check for possible dissolution of halite (why?); tritium and other anthropogenic contaminantsto exclude samples that contain bomb 36Cl (for what reason?); 14Cto select a number of samples that are very young in terms of the 36Cl half-life (what for?); Clto establish the initial 36Cl concentration in studied water samples (how?). Answer 12.6: The most important and most informative wells have to be selected for full analyses. The criteria will include the following: (a) at least ve samples to establish the local intake line (how will they be selected?); (b) the rest of the samples will be selected so that they include representatives of all water groups present (i.e., waters from different stratigraphic units, and hence possibly of different aquifers, and waters from the widest range of salinity); (c) wells with large yield are most important, as they represent larger portions of the exploited resource; (d) wells with much historical data (time series) are preferable, since the chance to understand their systems is greater if more auxiliary information is available. The well selection may be based on available data and complimentary preliminary measurements, most important being chlorine and, in unconned groundwaters, tritium. Answer 13.1: Using Fig. 13.1, the following values were abstracted for the solubility of the noble gases in air-saturated water, at sea level, expressed in cc STP/cc water:
Temperature 15 8C 22 8C 51 8C He 4.6 6 10 4.5 6 108 4.7 6 108

Ne 2.0 6 10 1.9 6 107 1.7 6 107


Ar 3.5 6 10 3.1 6 104 2.1 6 104




8.0 6 10 11.0 6 109 8 7.0 6 10 9.0 6 109 8 4.1 6 10 5.0 6 109

Answer 13.2: (a) The altitude correction factor at 1500 masl is 1.20 (Fig. 13.1).


Answers to Exercise Questions

(b) Solubility (5 8C, 0 m) (c) Solubility (5 8C, 1500 m)

He 4.9 6 108

Ne 2.2 6 107

Ar 4.4 6 104

Kr 11 6 108

Xe 16.5 6 109

He 4.1 6 108

Ne 1.8 6 107



Xe 13.8 6 109

3.7 6 104 9.2 6 108

All values are in cc STP/cc water.

Answer 13.3: (a) The average recharge altitude is (250 650)/2 450 masl; the respective altitude correction factor is 1.060; the Ar concentration normalized to sea level is 3:26104 61:060 3:46104 cc STP/cc water; the corresponding intake temperature is 15 8C. (b) 4 8C. (c) 10 8C. Answer 13.4: As it is a coastal spring and nothing is known about the recharge area, no altitude correction is to be applied. The intake temperature may be directly read from the argon concentration from Fig. 13.1. The outcome: 12 8C. Hence, the water was heated 32 8C 12 8C 20 8C. As the local heat gradient is not known, we shall use the common value of 3 8C/100 m. Accordingly, the minimum depth of circulation is 20 6 100/3 660 m. Answer 13.5: The neon curve in Fig. 13.1 is seen to vary little with temperature, and therefore it is of little use in intake temperature calculation. The argon curve is, in contrast, sensitive to temperature changes. An intake (base of aerated zone) temperature of 8 8C is obtained. Hence, 24 8C 8 8C 16 8C is the temperature gain obtained by circulation, reecting a distant and high intakethus indicating recharge from the mountain. If so, a respective altitude correction should be applied to the raw data, resulting in an intake temperature lower than 8 8C, further supporting mountain (and snowmelt) recharge. Answer 14.1: Placing the data into the equation, we get

t 266108 =107 60:8 1:2162 0:287626106 62:5610 43,000 years This is in the same order of magnitude of the reported 14C ages of the waters of group C.

Answers to Exercise Questions


Answer 14.2: Tritium, 14C, and 36Cl provide the base of three decaying dating methods, whereas 4He is the base of a cumulative dating method (and so is the yet poorly developed 40Ar method). In the rst group the ageindicating isotope concentrations are easy to measure at the young end of the age range, and in the second group the concentrations are easier to measure the older the samples are. Answer 14.3: The maximum helium concentration expectable in newly recharged water is read from the curve in Fig. 13.1 to be 56108 cc STP/cc water. Excesses over this concentration are of radiogenic helium. In groundwaters that have an age of over 10,000 years, this excess is signicant. Answer 14.4: There are two basic arguments: (1) in most rocks the helium age is found to be signicantly lower than the corresponding age dened by all other isotopic methods, indicating much of the radiogenic helium left the rock and (2) as the partial pressure of helium in the rock crystals increases with age, the amount expelled increases as well, until a steady state is reached at which the newly produced helium is fully balanced by the helium expelled into the associated groundwater. Answer 14.5: (a) Gas separation induced by pressure decrease during ascent in a wellcorrected for via the atmospheric Ne, Ar, Kr, and Xe that are lost by the same degree as the He, but their initial concentrations can be well estimated from assumed recharge altitude and ambient temperature; (b) mixing with recent (commonly shallow) groundwater, either in a spring or in a poorly cased welldetectable by disagreeing age indications, for example, detectable tritium or 14C together with appreciable concentrations of radiogenic He. Mixing corrections are discussed in sections 6.6 and 6.7. Answer 14.6: The ve diagrams report case studies in which the radiogenic helium concentration increases with depth (increase in temperature reects increase of depth). In general, deeper groundwaters reveal higher helium concentrations, interpreted as higher ages. The deeper groundwater systems in each study location are conned, and in general the older ones were deeper buried during basin subsidence. Deviations from the general positive correlation may reect varying concentrations of uranium and thorium and different rock:water ratios. Answer 14.7: The following patterns are seen in Fig. 14.2: (a) the line segments of Ne to Xe have a similar general pattern for all water samples, resembling the shape of the line of water saturated with air at 15 8C (ASW 15 8C); thus the respective Ne, Ar, Kr, and Xe concentrations originate from initially dissolved air. (b) The concentrations of the dissolved


Answers to Exercise Questions

atmospheric Ne, Ar, Kr, and Xe vary from one sample to the other over one-and-one-half orders of magnitude, with different degrees of gas losses or gains. (c) In contrast, the He data are all signicantly higher than in the air-saturated water, indicating the presence of radiogenic He in all the studied samples. Answer 14.8: The data were normalized to the concentrations in the approximated recharge water, presented by the ASW line (see the location of this line in the diagram). This mode of noble gas data representation reveals that a few samples almost retained all their initial atmospheric noble gases, others retained as little as 20%, and two samples reveal enrichments, possibly from air added during sample collection (for such reasons duplicate and even triplicate samples should be collected from each well and measured). Answer 15.1: The Curiosity 1 well taps stagnant groundwater, because at a depth of 105 m 15 m 90 m below sea level, groundwater is in the zone of zero hydraulic potential, and the water is expected to be stagnant. The age of around 17,000 years indicates recharge during the last glacial maximum. At that time the sea level was substantially lower (by how much can, in most places, be learned from other studies). The ancient water table was accordingly lower. The following climatic warming was accompanied by ice melting and a rise in the sea to its present level. Thus the presently active through-ow system, tapped by the shallow well, lies above the ancient groundwater. Answer 15.2: Probably not. As the d13C value was 8.1%, it was concluded that the water reacted mainly with the local marine limestone, and an initial 14C concentration of 65 pmc was applied for the age calculation, with no d13C correction (section 11.7). The similarity of the d13C values in the ancient and recent groundwaters revealed that, most probably, no change in the plant community occurred. Answer 15.3: Yes, the water sampled from the deep well could be a mixture of water from different depths if the casing was corroded (section 11.10). In such a case the sampled water would be a mixture of different ages, and the calculated age would be meaningless. To check this possibility, data on the concentration of tritium and other anthropogenic pollutants are needed. If the latter are not present, the water is most probably not a mixture. Answer 15.4: Yes, the chemical and isotopic composition should be established in the deep well and in the adjacent shallow well. This should be done in repeatedly collected samples under different pumping rates (with the

Answers to Exercise Questions


aid of a portable pump). The following possibilities are envisaged: (a) The chemical composition of the water in the two wells is signicantly different, in which case mixing can be checked. (b) The dissolved ion concentrations in the deep well will be similar to those in the shallow well, in which case the chemistry will not serve as a mixing indicator. But, (c) the isotopic composition is expected to differa lighter composition is expected in the older water as the age coincides with the last ice age. In the last case the stable isotopes may serve as mixing indicators: if the chemical composition does not change and the lighter isotopic composition is repeated in the samples collected in the deep well under different pumping rates, the deep water is conclusively not a mixture. Answer 15.5: Yes, it seems ideal, as it provides an unmixed sample of an established age, coinciding with the last glacial maximum (i.e., a phase of an extreme climate). A higher concentration of the heavier atmospheric noble gases is expected, and if found, it will support the colder climate reconstruction. Answer 15.6: Since the present climate is temperate and the location is in the coastal plain, it seems safe to conclude that even during the glacial maximum no snow line came near the paleorecharge location. Hence, no snowmelt was involved, and the deduced paleotemperature is the average ambient one. To be safe in this point, it is worth studying the setup of the shallow well. If the present recharge is through a porous aerated zone, and not karstic, then the conclusion that one deals with the average ambient paleotemperature is supported. Answer 16.1: The observed nitrate contamination was attributed to extensive use of nitrate fertilizers. This hypothesis has to be checked using the following steps: Conduct a survey of adjacent agricultural activitieswhere are fertilizers used? What types of fertilizers are used? How long have they been in use? From the above, make a list of compounds that are introduced into the ground along with each type of applied fertilizer (e.g., K, SO4). These compounds should be analyzed, along with nitrate, in accessible wells in depth proles of the type shown in Fig. 16.1. Answer 16.2: No, the injected brine might have contained petroleum compounds that could be adsorbed in the aquifer rocks and be slowly released into the groundwater. Hence, petroleum contaminants, and not just chlorine, should be analyzed in the damaged groundwater.


Answers to Exercise Questions

Answer 16.3: The monitoring operation cannot be stopped, and the following steps have to be undertaken: (a) The water in the ash pit should be measured periodically for possible changes. (b) The water in the ash pit should be analyzed for a large number of possible toxic compounds, especially trace metals. (c) The detailed analyses of the pit water should be used to search for more sensitive tracers. (d) The conclusion, based on wells A and C, that the pit water was well conned, was based on the assumption that water moves in a granular medium with no conduitcontrolled ow. This might either have been wrong from the beginning, or conduit ow may have evolved due to water leaking from the pit. Hence, monitoring is always needed. The composition of the water in the ash pit looked harmless from the data given in Table 16.3. It is the additional analyses, recommended for this water, that will determine whether it is really harmless or whether some toxic compounds exist, necessitating more careful monitoring. Answer 16.4: The leachate monitored by the piezometers located in the pit revealed that a threat to local groundwater exists. (What are the concentrations of the various ions?) A plume of leachate entering the local groundwater is observed in the direction of the water level gradient. Contamination is noticeable at a distance of how far (use the scale of the maps)? The mentioned observation that metals found in the leachate do not show up in the monitoring wells is explainable by adsorption on clay material in the soil. However, this means that a hallow of metals is formed in the soil and it may reach local groundwater in the future. Therefore, metals observed in the leachate should be measured periodically in the monitoring wells. Answer 17.1: Cessation of groundwater drainage also means cessation of washing away salts and pollutants, so these will accumulate in the coastal groundwater system and the latter will deteriorate. Answer 17.2: No, it is conned by the overlying rocks. The advantage is that it has no contact with the land surface, and hence it is not vulnerable to anthropogenic pollutionmaking it a suitable reserve for use in cases of large-scale pollution catastrophes (section 17.8.5). Answer 17.3: That man exploits a little less than the amount that is renewed, e.g., pumping so that some groundwater still drains to the ocean. And, second, that man does not deteriorate surface and groundwater systems by irreversible contamination. Answer 17.4: Along the lines discussed in section 17.9.2.

Answers to Exercise Questions


Answer 17.5: Yes, potential polluting installations are better located at the groundwater downow side of the city (section 17.9.4). Answer 18.1: (a) Why are they needed? (b) Which considerations lead the committees that set the standards? (c) What can cause deviations that are nonhealthy? Are you familiar with these points? Can you present them? Answer 18.2: They are described in section 18.1.2.

Answer 18.3: At the groundwater downow direction. Why not at the upow direction? Answer 18.4: A station at each river tributary before it reaches the main river and a number of stations along the main river. Does this make sense? Answer 18.5: Partially, piezometers 5 and 6 monitor the very shallow groundwater and two river stations monitor in the downow direction, but the nearest water wells are 5 to 7 km away. Answer 18.6: They run along maximum wells that provide the data needed for the cross-sections. Answer 18.7: The effect of forest clearing. What is the observation? What is the conclusion in this case? Answer 18.8: For exhibitions and teaching in regions that are close to an oil production eld. What is the observation? What is the conclusion in this case?


Textbooks for further reading are marked by an asterisk (*), and special texts published by the International Atomic Energy Agency are given at the end of this list.
Adar, E. (1984) Quantication of aquifer recharge distribution using environmental isotopes and regional hydrochemistry (Ph.D. diss.) Dept. of Hydrology and Water Resources, University of Arizona, Tucson. Allison, G.B. and Hughes, M.W. (1975) The use of environmental tritium to estimate recharge to a South-Australian aquifer. J. of Hydrology 26, 245254. Andersen, L.J., Kelstrup, V., and Kristiansen, H. (1980) Chemical proles in the Karup water-table aquifer, Denmark. In: Nuclear Techniques in Groundwater Pollution Research, IAEA, Vienna, 4760. Andrews, C.B. and Anderson, M.P. (1978) Impact of a power plant on the groundwater system of a wetland. Groundwater 16, 105111. Andrews, J.N. and Lee, D.J. (1979) Inert gases in groundwater from the Bunter sandstone of England as indictors of age and paleoclimatic trends. J. of Hydrology 41, 233252. Andrews, J.N., Giles, I.S., Kay, R.L.F., Lee, D.J., Osmond, J.K., Cowart, J.B., Fritz, P., Barker, J.F. and Gale, J. (1982) Radioelements, radiogenic helium and age relationships for groundwaters from the granites at Stripa, Sweden. Geochimica et Cosmochimica Acta 46, 15331543. Andrews, J.N., Balderer, W., Bath, A.H., Clausen, H.B., Evans, G.V., Florkowski, T., Goldbrunner, J.E., Ivanovich, M., and Loosli, H. (1984) Environmental isotope study in two aquifer systems. In: Isotope Hydrology 1983, IAEA, Vienna 535576.




Andrews, J.N., Goldbrunner, J.E., Darling, W.G., Hooker, P.J., Wilson, G.B., Youngman, M.J., Eichinger, L., Rauert, W., and Stichler, W. (1985) A radiochemical, hydrochemical and dissolved gas study of groundwaters in the Molasse basin of upper Austria. Ear and Planetary Sci. Lett. 73, 317 332. Andrews, J.N., Youngman, M.J., Goldbrunner, J.E., and Darling, W.G. (1987) The Arad, A., Kafri, U., Halicz, L., and Brenner, I. (1984) Chemical composition of some trace and minor elements in natural groundwaters in Israel. Geol. Survey Israel, Rep. 29/84. Back, W. and Hanshaw, B.B. (1970) Comparison of chemical hydrogeology of the carbonate peninsulas of Florida and Yucatan. J. of Hydrology 10, 330 368. Balderer, W. (1985) Sondierbohrung Bottstien: Rrgebnisse der Isotopenuntersuchungen zur hydrogeologischen Charakterisierung der Tiefengrundwasser. National Genosenchaft fur die Lagerung Radioaktiver Abfale (NAGRA) Baden, Switzerland, Technischer Bericht, 8560. Bath, A.H., Edmunds, W.M., and Andrews, J.N. (1979) Paleoclimatic trends deduced from the hydrochemistry of a Triassic sandstone aquifer, United Kingdom. In: Isotope Hydrology 1978, IAEA, Vienna, 545568. Bebout, D.G. and Gutierrez, D.R. (1981) Geopressured geothermal resources in Texas and Louisianageological constraints. Proc. 5th Conf. GeopressuredGeothermal Energy, Baton Rouge, Louisiana, 1324. Bentley, H.W. and Davis, S.N. (1980) Isotope geochemistry as a tool for determining regional groundwater ow. Proc. 1980 National Terminal Storage Program Information Meeting, Columbus, Ohio, 3541. Bentley, H.W., Phillips, F.M., Stanley, N.D., Habermehl, M.A., Airey, P.L., Calf, G.E., Elmore, D., Gove, H.E. and Torgersen, T. (1986a) Chlorine-36 dating of very old groundwater 1. The Great Artesian Basin, Australia. Water Resourc. Res. 22, 19912001. Bentley, H.W, Davis, S.N., Elmore, D., and Swanick, G.B. (1986b): Chlorine-36 dating of very old groundwater 2. Milk River Aquifer, Canada. Water Resourc. Res. 22, 20032016. Bentley, H.W., Phillips, F.M., and Stanley, N.D. (1986c) Chlorine-36 in the terrestrial environment. In: Handbook of Environmental Isotope Geochemistry, vol. 1B, 442475. Bird, J.R., Calf, G.E., Davie, F.F., Field, L.K., Ophel, T.R., Evans, W.R., Kellett, J.R., and Habermehl, M.A. (1989) The role of 36Cl and 14C measurements in Australian groundwater studies. Radiocarbon 31(3). Borman, F.H. and Likens, G.E. (1970) The nutrient cycles of an ecosystem. Sci. A. 223(4), 92101. Borole, D.V., Gupta, S.K., Krishnaswami, S., Datta, P.S., and Desai, B.I. (1979) Uranium isotopic investigations and radiocarbon measurements of river-groundwater systems, Sabaramati Basin, Gujarat, India. In: Isotope Hydrology 1978, IAEA, Vienna, 1, 181201.



Bortolami, G.C., Ricci, B., Suzella, G.F., and Zuppi, G.M. (1978) Isotope hydrology of the Val Coraoglia, Maritime Alps, Piedmont, Italy. In: Isotope Hydrology, IAEA, Vienna, 327350. Bosch, A. (1990) Atmospheric and non-atmospheric noble gases in the geohydroderm (Ph.D. diss.), Weizmann Institute of Science, Rehovot, Israel. Bradley, J.S. and Powly, D.E. (1994) Pressure compartments in sedimentary basins: a review. In: Basin Compartments and Seals, Ortoleva, P.J. (ed.); American Association of Petroleum Geologists, Memoir 61, Tulsa, Oklahoma, 326. *Brassington, R. (1988) Field Hydrology. Open University Press, Milton Keynes; Halsted Press John Wiley, New York. Bredenkamp, D.B., Schutte, J.M., and Du Toit, G.J. (1974) Recharge of a dolomitic aquifer as determined from tritium proles. In: Isotope Techniques in Groundwater Hydrology 1974. IAEA, Vienna, 1, 7396. Broecker, W.S. (1986) Oxygen isotope constraints on surface ocean temperatures. Quaternary Res. 26, 121134. Calf, G.E., Bird, J.R., and Evans, W.R. (1988) Origins of chloride variation in the Murray Basin using environmental Cl-36 (abstract). Conference on Studies in Hydrology, Murray Basin, Canberra, 2326 May 1988. *Carter, M.W., Moghissi, A.A., and Kahn, B. (eds.) (1979) Management of LowLevel Radioactive Wastes. Pergamon Press, Oxford. Castany, G. (1960) Quelques aspects nouveaux de lhydrogeologie du basin parisien. C.R. ann. Comite Fr. Geol. Geoph. Cherkauer, D.S. (1980) The effect of yash disposal on a shallow groundwater system. Ground Water 18, 544550. Conrad, G., Jouzel, J., Merlivat, L., and Puyoo, S. (1979) La nappe de la craie en Haute-Normandie (France) et ses relations avec les eaux supercielles. In: Isotope Hydrology 1978, IAEA, Vienna, 1, 265287. Cotecchia, V., Tuzioli, G.S., and Magri, G. (1974) Isotopic measurements in research on seawater ingression in the carbonate aquifer of the Salentine Peninsula, Southern Italy. In: Isotope Techniques in Groundwater Hydrology 1974, IAEA, Vienna, 1, 445463. Craig, H. (1961a) Isotopic variations in meteoric waters. Science 133, 17021703. Craig, H. (1961b) Standard for reporting concentrations of deuterium and oxygen-18 in natural waters. Science 133, 18331834. Dansgaard, W. (1964) Stable isotopes in precipitation. Tellus 16, 436469. Davie R.F., Field, L.K., Bird, J.R., Ophel, T.R., and Calf, G.E. (1988) The application of 36Cl measurements to groundwater modeling (abstract 4750). Conference on studies in Hydrology, Murray Basin, Canberra, 2326 May 1988. Davie R.F., Kellett, J.R., Field, L.K., Evans, W.R., Calf, G.E., Bird, J.R., Topham, S., and Ophel, T.R. (1989) Chlorine-36 measurements in the Murray Basin: preliminary results from the Victorian and South Australian Mallee region. J. Australian Geophys. 11, 261272. Davis, S.N. and Bentley, H.W. (1982): Dating groundwater, a short review. In: Nuclear and Chemical Dating Techniques: Interpreting the Environmental Record, Currie L.A. (ed.), American Chemical Society Symp. Series 176, 187222.



*Davis, S. and DeWiest, R.J.M. (1966) Hydrogeology. John Wiley, New York. Deak, J. (1979) Enviromental isotopes and water chemical studies for groundwater research in Hungary. In: Isotope Hydrology 1978, IAEA, Vienna, 1, 221249. Deak, J., Stute, M., Rudolph, J., and Sonntag, C. (1987) Determination of the ow regime of Quaternary and Pliocene layers in the Great Hungarian Plain (Hungary) by D, 18O, 14C and noble gas measurements. In: Isotope Techniques in Water Resources Development, IAEA, Vienna, 335350. De Marsily, G. (1986) Quantitative Hydrology. Academic Press, New York. Dennis, H.W. (1973) Salt pollution of a shallow aquifer, Indianapolis, Indiana. Ground Water 11, 1822 Dowing, R.A., Smith, D.B., Pearson, F.J., Monksouse, R.A., and Otlet, R.L. (1977) The age of groundwater and its relevance to the ow mechanism. J. of Hydrology 33, 201216. *Drever, J.I. (1982) The Geochemistry of Natural Waters. Prentice-Hall, Englewood Cliffs, N.J. *Eriksson, E. (1985) Principles and Application of Hydrochemistry. Chapman and Hall, London. Evin, J. and Vuillaume, Y. (1970) Etude par le radiocarbone de la Nappecaptive de LAlbien du Bassin de Paris. In: Isotope Hydrology 1970, IAEA, Vienna, 315332. Fontes, J.Ch. (1983) Dating of Groundwater. Guide on Nuclear Techniques in Hydrology. Technical Reports Series no. 91, IAEA, Vienna, 285. Fontes, J.Ch., Bortolami, G.C., and Zuppi, G.M. (1979) Isotope hydrology of the Mont Blanc Massif. In: Isotope Hydrology 1978, IAEA. Vienna, 411436. Foster, K.E. and Fogel, M.M. (1973) Mathematical modelling of soil temperature. Progressive Agriculture in Arizona 25, 1012. *Freeze, R.D. and Cherry, A. (1979) Groundwater. Prentice-Hall, Englewood Cliffs, N.J. Fridman, V., Mazor, E., Becker, A., Avraham, D., and Adar, E. (1995) Stagnant aquifer concept: III. Stagnant mini-aquifers in the stage of formation, Makhtesh Ramon, Israel. J. of Hydrology 173, 263282. *Fritz, P. and Fontes, J.Ch. (eds.) (1980 and 1986) Handbook of Environmental Isotope Geochemistry. Vols. 1 and 2. Fritz, P., Drimmie, R.J., and Render, F.W. (1974) Stable isotope contents of a major prairie aquifer in central Manitoba, Canada. In: Isotope Techniques in Groundwater Hydrology 1974, IAEA, Vienna, 1, 379398. Fritz, P., Matthess, G., and Brown, R.M. (1976) Deuterium and oxygen-18 as indicators of leachwater movement from a sanitary landll. In: Interpretation of Environmental Isotope and Hydrochemical Data in Groundwater Hydrology, IAEA, Vienna, 131142. Fritz, P., Hennings, C.S., Suzolo, O., and Salati, E. (1979) Isotope hydrology in northern Chile. In: Isotope Hydrology 1978, IAEA, Vienna, 2, 525544. Fryberger, J.F. (1975) Investigation and rehabilitation of a brine contaminated aquifer. Ground Water 13, 155160. Gat, J.R. (1971) Comments on the stable isotope method in regional groundwater investigations. Water Resourc. Res. 7, 980993.



Gat, J.R. and Dansgaard, W. (1972) Stable isotope survey of the fresh water occurences in Israel and the Northern Jordan Rift Valley. J. of Hydrology 16, 177212. Gat, J.R., Mazor, E., and Tzur, Y. (1969) The stable isotope composition of mineral waters in the Jordan Rift Valley, Israel. J. of Hydrology 7, 334352. Geyh, M.A. (1972) Basic studies in hydrology and 14C and 3H measurements. 24th Int. Geol. Cong., Montreal, 2, 227234. Geyh, M.A. (1980) Interpretation of environmental isotopic groundwater data, arid and semi-arid zones. In: Arid-Zone Hydrology: Investigations with Isotope Techniques, IAEA, Vienna, 3146. Geyh, M.A. and Wirth, K. (1980) 14C ages of conned groundwater from the Gwandu aquifer, Sokoto basin, Northern Nigeria. J. of Hydrology 48, 281 288. Goldenberg, L.C., Margaritz, M., and Mandel, S. (1983) Experimental investigation of irrevesible changes of hydraulic conductivity on the seawaterfreshwater interface in coastal aquifers. Water Resourc. Res. 19, 7785. Gonantini, R., Dincer, T., and Derekoy, A.M. (1974) Environmental isotope hydrology in the Honda region, Algeria. In: Isotope Techniques in Groundwater Hydrology 1974, IAEA, Vienna, 1, 293316. Goolsby, D.A. (1971) Hydrochemical effects of injecting wastes into a limestone aquifer near Pensacola, Florida. Ground Water 9, 1319. Habermehl, M.A. (1980) The Great Artesian Basin, Australia. BMR J. Australian Geol. Geophys. 5, 938. Heaton, T.H.E. (1984) Rates and sources of 4He accumulation in groundwater. Hydrology Sci. J. 29, 2947. Heaton, T.H.E. and Vogel, J.C. (1981) Excess air in groundwater. J. of Hydrology 50, 201216. *Hem, J.D. (1985) Study and Interpretation of the Chemical Characteristics of Natural Water. U.S. Geological Survey, Water Supply Paper 254. Herczeg, A.L., Simpson, H.J., and Mazor, E. (1993) Transport of soluble salts in a large semiarid basin: River Murray, Australia. J. of Hydrology 144, 59 84. Herzberg, O. and Mazor, E. (1979) Hydrological applications of noble gases and temperature measurements in underground water systems, examples from Israel. J. of Hydrology 41, 217231. Hubbert, M.K. (1940) The theory of ground-water motion. J. of Geology 48(8), 785 944. Hufen, T.H., Lau, L.S., and Buddemeier, R.W. (1974) Radiocarbon, 13C and tritium in water samples from basaltic aquifers and carbonate aquifers on the island of Oahu, Hawaii. In: Isotope Techniques in Groundwater Hydrology 1974, IAEA, Vienna, 2, 111127. *Hutton, L.G. (1983) Field Testing of Water in Developing Countries. Water Research Centre, Medmeham, England. Jorgensen, D.G. (1968) An aquifer test used to investigate a quality of water anomaly. Ground Water 6, 1820.



Kroitoru, L. (1987) The characterization of ow systems in carbonatic rocks dened by the groundwater parameters: Central Israel (Ph.D. diss.), Feinberg Graduate School of the Weizmann Institute of Science, Rehovot, Israel. Kroitoru, L., Carmi, I., and Mazor, E. (1987) Groundwater 14C activity as affected by initial waterrock interactions in a carbonatic terrain with deep water tables: Judean Mountains, Israel. Int. Symp. on the Use of Isotope Techniques in Water Resources Development, IAEA, Vienna, extended abstract, 134136. Leontiadis, I.L., Payne, B.R., Letsios, A., Papagianni, N., Kakarelis, D., and Chadjiagorakis, D. (1983) Isotope hydrology study of Kato Nevroko of Dramas. In: Isotope Hydrology 1983, IAEA, Vienna, 193206. Levy, Y. (1987) The Dead Sea, hydrographic, geochemical and sedimentological changes during the last 25 years (19591984). Geological Survey of Israel (in Hebrew). Lewallen, M.J. (1971) Pesticide contamination of a shallow bored well in southeastern Coastal Plains. Ground Water 9, 4549. Loosli, H.H. and Oeschger, H. (1978) 39Ar, 14C and 85Kr measurements in groundwater samples. In: Isotope Hydrology 1978, IAEA, Vienna, 2, 931997. Love, A.J., Hreczeg, A.L., Armstrong, D., Stadter, F., and Mazor, E. (1993) Ground-water ow regime within the Gambier Embayment of the Otway Basin, Australia: evidence from hydraulics and hydrochemistry. J. of Hydrology 143, 297338. Marine, I.W. (1979) The use of naturally occurring helium to estimate groundwater velocities for studies of geologic storage of radioactive waste. Waste Resourc. Res. 15, 11301136. Martinsen, R.S., (1994) Summary of published literature on anomalous pressure: implications for the study of pressure compartments. In: Basin Compartments and Seals, Ortoleva, P.J. (ed.), AAPG Memoir 61, American Association of Petroleum Geologists, Tulsa, Oklahoma, 477. Marty, B., Criaud, A., and Fouillac, C. (1988) Low enthalpy geothermal uids from the Paris sedimentary basin1. Characteristics and origin of gases. Geothermics 17, 619633. *Matthes, G. (1982) The Properties of Groundwater. John Wiley, New York. Mazor, E. (1972) Paleotemperatures and other hydrological parameters deduced from noble gases dissolved in groundwaters: Jordan Rift Valley, Israel. Geochim. et Cosmochim. Acta 36, 13211336. Mazor, E. (1975) Atmospheric and radiogenic noble gases in thermal waters: their potential application to prospecting and steam production studies. Proc. 2nd UN Symp. on Development and Use of Geothermal Resources, San Francisco, 1, 793 801. Mazor, E. (1976) Multitracing and multisampling in hydrological studies. In: Interpretation of Environmental Isotope and Hydrochemical Data in Groundwater Hydrology, IAEA, Vienna, 736. Mazor, E. (1978) Mineral waters of the Kinneret basin and possible origin. In: A Monography on Lake Kinneret, Serruya, C. (ed.), W. Junk N.V. Publishers, The Hague, 103120.



Mazor, E. (1979a) Dilute waterrock reactions in shallow aquifers of the Kalahari atland. Proc. 3rd WaterRock Interaction Symp., Edmonton, Canada, 14 15. Mazor, E. (1979b) Noble gases in a section across the vapour dominated geothermal eld in Larderello, Italy. Pure and Applied Geophys. 117, 262275. Mazor, E. (1982) Rain recharge in the Kalaharia note on some approaches to the problem. J. of Hydrology 55, 137144. Mazor, E. (1985) Mixing in natural and modied groundwater systems: detection and implications on quality and management. In: Scientic Basis for Water Resources Management. IAHS Publ. no. 153, 241251. Mazor, E. (1986) Chemical, isotopic and physical data used to check basic (commonly assumed) hydrological interrelations. Proc. Int. Conf. on Groundwater Systems Under Stress, Brisbane, Australia, May 1986, 114. Mazor, E. (1992a) He as a semi-quantitative tool for groundwater dating in the range of 104 to 108 years. In: Isotopes of Noble Gases as Tracers in Environmental Studies, IAEA, Vienna, 163178. Mazor, E. (1992b) Reinterpretation of Cl-36 data: physical processes, hydraulic inter-connections, and age estimates in groundwater systems. Applied Geochem. 7, 351360. Mazor, E. (1993a) Chlorine-36 data and basic concepts of hydrologycomments on F.M. Phillips comment, with special reference to the Great Artesian Basin. Applied Geochem. 8, 649651. Mazor, E. (1993b) Interrelations between groundwater dating, paleoclimate and paleohydrology. In: Applications of Isotope Techniques in the Study of Past and Current Environmental Changes in the Hydrosphere and the Atmosphere, IAEA, Vienna, 249257. Mazor, E. (1993c) The need for auxiliary data to address the long list of processes recruited to interpret 36Cl data in groundwater systemsa reply to the comment by J.C. Fontes and J.N. Andrews. Applied Geochem. 8, 667669. Mazor, E. (1993d) Some basic principles of 36Cl hydrologya reply to the discussion by Kellett, Evans, Allan, and Field. Applied Geochem. 8, 659662. Mazor, E. (1995) Stagnant aquifer concept I. Large scale artesian systemsGreat Artesian Basin, Australia. J. of Hydrology 174, 219240. Mazor, E. and Bosch, A. (1987) Noble gases in formation uids from deep sedimentary basins: a review. Applied Geochem. 2, 621627. Mazor, E. and Bosch, A. (1990) Dynamics of groundwater in deep basins: He-4 dating, hydraulic discontinuities and rates of drainage. International Conference on Groundwater in Large Sedimentary Basins, Perth, Western Australia, 913 July 1990. Department of Primary Industries and Energy Proc., 380389. Mazor, E. and Bosch, A. (1992a) He as a semi-quantitative tool for groundwate dating in the range of 104 to 108 years. In: Isotopes of Noble Gases as Tracers in Environmental Studies, IAEA, Vienna, 163178. Mazor, E. and Bosch, A. (1992b) Physical processes in geothermal systems derived by noble gases. In: Isotopes of Noble Gases as Tracers in Environmental Studies, IAEA, Vienna, 203218.



Mazor, E. and George, R. (1992) Marine airborne salts applied to trace evapotranspiration, local recharge and lateral groundwater ow in Western Australia. J. of Hydrology 139, 6377. Mazor, E. and Kroitoru, L. (1987) Phreatic-conned discontinuities and restricted ow in conned groundwater systems. Int Symp. on the Use of Isotope Techniques in Water Resources Development, IAEA, Vienna, extended abstract, 130131. Mazor, E. and Kroitoru, L. (1992) Beer ShevaYarkonTaninim: one groundwater group or several separate ones? Israel Bull. Earth Sci. 39, 6770. Mazor, E. and Mero, F. (1969a) Geochemical tracing of mineral and fresh water sources in the Lake Tiberias basin, Israel. J. of Hydrology 7, 276317. Mazor, E. and Mero, F. (1969b) The origin of the Tiberias-Noit mineral water association in the TiberiasDead Sea Rift Valley, Israel. J. of Hydrology 7, 318 333. Mazor, E. and Nativ, R. (1992) Hydraulic calculation of groundwater ow velocity and age: examination of the basic premises. J. of Hydrology 138, 211222. Mazor, E. and Nativ R., (1994) Stagnant groundwaters stored in isolated aquifers: implications related to hydraulic calculations and isotopic datinga reply to a comment by T. Torgersen. J. of Hydrology, 154, 409418. Mazor, E. and Truesdell, A.H. (1984) Dynamics of a geothermal eld traced by noble gases: Cerro Prieto, Mexico. Geothermics, 13, 91102. Mazor, E. and Verhagen, B.Th. (1983) Dissolved ions, stable isotopes and radioactive isotopes and noble gases in thermal waters of South Africa. J. of Hydrology 63, 315329. Mazor, E. and Wasserburg, G.J. (1965) Helium, neon, argon, krypton and xenon in gas emanation in Yellowstone and Lassen Volcanic National Parks. Geochim. et Cosmochim. Acta 29, 443454. Mazor, E., Rosenthal, E., and Eckstein, J. (1969) Geochemical tracing of mineral water sources in the South-Western Dead Sea Basin, Israel. J. of Hydrology 7, 246275. Mazor, E., Kaufman, A., and Carmi, I. (1973a) Hammet Gader (Israel): geochemistry of a mixed thermal spring complex. J. of Hydrology 18, 289303. Mazor E., Nadler, A., and Harpaz, Y. (1973b) Notes on the geochemical tracing of the Kaneh-Samar spring complex, Dead Sea basin. Israel J. of Earth Sci. 22, 255 262. Mazor, E., Verhagen, B.Th., and Negrenenu, E. (1974) Hot springs of the igneous terrain of Swaziland. In: Isotope Techniques in Groundwater Hydrology 1974, IAEA, Vienna, 2, 2947. Mazor, E., Verhagen, B.Th., Sellschop, J.P.F., Jones, M.T., Robins, N.E., Hutton, L., and Jennings, C.M.H. (1977) Northern Kalahari groundwaters: hydrologic, isotopic and chemical studies at Orapa, Botswana. J. of Hydrology 34, 203234. Mazor, E., Verhagen, B.Th., Sellschop, J.P.F., Jones, M.T., and Hutton, L.C. (1981) Sodium exchange in a NaCl waste disposal case (Lobatse, Botswana): implications to mineral water studies. Environ. Geol. 3, 195199.



Mazor, E., Vautax, F.D., and Jaffe, F.C. (1985) Tracing groundwater components by chemical, isotopic and physical parameters, example: Schinziach, Switzerland. J. of Hydrology 76, 233246. Mazor, E., Jaffe, F.C., Fluck, J., and Dubois, J.D. (1986) Tritium corrected C-14 and atmospheric noble gas corrected He-4, applied to deduce ages of mixed groundwaters: examples from the Baden region, Switzerland. Geochim. et Cosmochim. Acta 50, 16111618. Mazor, E., Dubois, J.D., Soom-Fluck, J., and Wexsteen, P. (1990) Time-data series as a major diagnostic tool in groundwater hydrology: case studies from Switzerland II. International Conference on Water Resources in Mountainous Regions, IAH and IAHS, Lausanne, Switzerland, Memoires of the 22nd Congress of IAH, vol. XXII, 281288. Mazor, E., Vautaz, F.D., and Jaffe, F.C., (1990) Time-data series as a major diagnostic tool in groundwater hydrology: case studies from Switzerland I. International Conference on Water Resources in Mountainous Regions, IAH and IAHS, Lausanne, Switzerland, Memoirs of the 22nd Congress of AIH, vol. XXII, 271280. Mazor, E., Drever, J.I., Finely, J., Huntoon, P.W., and Lundy, D.A. (1992) Hydrochemical implications of groundwater mixing: an example from the southern Laramie Basin, Wyoming. Water Resourc. Res. 29, 193205. Mazor, E., Gilad, D., and Fridman, V. (1995) Stagnant aquifer concept: II. Smallscale artesian systemsHazeva, Dead Sea Rift Valley, Israel. J. of Hydrology 173, 241261. *Ozima, M. and Podosek, F.A. (1983) Noble Gas Geochemistry. Cambridge University Press, Cambridge. Payne, B.R. and Yurtsever, Y. (1974) Environmental isotopes as a hydrogeological tool in Nicaragua. In: Isotope Techniques in Groundwater Hydrology 1974, IAEA, Vienna, 1, 193202. Payne, B.R., Quijano, L., and Latorred, C.D. (1980) Study of the leakage between two aquifers in Hermosillo, Mexico, using environmental isotopes. In: Arid-Zone Hydrology: Investigations with Isotope Techniques, IAEA, Vienna, 113130. Pearson, Jr., F.J. and Hanshaw, B.B. (1970) Sources of dissolved carbonate species in groundwater and their effects on carbon-14 dating. In: Isotope Hydrology 1970, IAEA, Vienna, 271286. Pearson, F.J. and Swarzenski, W.V. (1974) 14C evidence for the origin of arid region groundwater, northeastern province, Kenya. In: Isotope Techniques in Groundwater Hydrology 1974, IAEA, Vienna, 2, 95109. Pearson, G.N. (1974) Tritium data from groundwater in the Kristianstad plain, southern Sweden. In: Isotope Techniques in Groundwater Hydrology 1974, IAEA, Vienna, 1, 4556. Phillips, F.M., Benrley, H., Davis, S.N., Elmoer, D., and Swanick, G.B. (1986) Chlorine-36 dating of very old groundwater 2. Milk River Aquifer, Alberta, Canada. Water Resourc. Res. 22, 20032016.



Pickens, J.F., Cherry J.A., Grisak, G.E., Merritt, W.F., and Risto, B.A. (1978) A multilevel device for ground-water sampling and piezometric monitoring. Ground Water 16, 322327. Podosek, F.A., Honda, M. and Ozima, M. (1980) Sedimentary noble gases. Geochimica et Cosmochimica Acta 44, 18751884. Rafter, T.A. (1974) The dating of fossil man in Australia. Proc. Symp. Hydrogeochemistry and Biogeochemistry, Tokyo, Japan. Rudolph, J., Rath, H.K., and Sonntag, C. (1983) Noble gases and stable isotopes in 14 C-dated paleowaters from central Europe and the Sahara. In: Isotope Hydrology 1983, IAEA, Vienna, 467477. Safnga, P.G. and Keeney, D.R. (1977) Nitrate and chloride in ground water irrigated agriculture in Central Wisconsin. Ground Water 15, 170177. Salati, E., Matsui, E., Leal, J.M., and Fritz, P. (1980) Utilization of natural isotopes in the study of salinization of the waters in the Pajeu River Valley, northeast Brazil. In: Arid-Zone Hydrology: Investigations with Isotope Techniques, IAEA, Vienna, 133151. Schlosser, P., Stute, M., Dorr, H., Sonntag, C., and Munich, K.O. (1988) Tritium/3He dating of shallow groundwater. Earth and Planetary Sci. Lett. 89, 353362. Schoch-Fischer, H., Rozanski, K., Jacob, H.J., Sonntag, C., Jouzel, I., Ostlund, G., and Geyh, M.A. (1983) Hydrometeorological factors controlling the time variation of D, 18O and 3H in atmospheric water vapour and precipitation in the northern westwind belt. In: Isotope Hydrology 1983, IAEA, Vienna, 330. Schoeller, H. (1954) Arid Zone HydrologyRecent Developments. UNESCO, Paris. Shampine, W.J., Dincer, T., and Noory, M. (1979) An evaluation of isotope concentrations in the groundwater of Saudi Arabia. In: Isotope Hydrology 1978, IAEA, Vienna, 2, 443463. Shuster, E.T. and White, W.B. (1971) Seasonal uctuations in the chemistry of limestone springs: a possible means for characterizing carbonate aquifers. J. of Hydrology 14, 93128. Siegenthaler, U. and Oeschger, H. (1980) Correlation of 18O in precipitation with temperature and altitude. Nature 285, 314317. Sonntag, C., Klitzsch, E., Lohnert, E.P., Ee-Shazly, E.M., Munnich, K.O., Junghans, Ch., Thorweihe, U., Weistroffer, K., and Swailem, F.M. (1979) Paleoclimatic information from deuterium and oxygen-18 in carbon-14 dated north Saharian groundwaters. In: Isotope Hydrology 1978, IAEA, Vienna, 2, 569 581. *Stahl, W., Aust, H., and Dounas, A. (1974) Origin of artesian and thermal waters determined by oxygen, hydrogen and carbon isotope analyses of water samples from the Sperkhios Valley, Greece. In: Isotope Techniques in Groundwater Hydrology 1974, IAEA, Vienna, 1, 317339. Stute, M., Forster, H., Frischkorn, A., Serejo, Clark, J.F., Schlosser, P., Broecker, W.S., and Bonani, G. (1995a) Cooling of tropical Brazil (58 C) during the last glacial maximum. Science 269, 379383.



Stute, M., Clark, J.F., Schlosser, P., Broecker, W.S., and Bonani, G. (1995b) A 10,000-yr continental paleotemperature record derived from noble gases dissolved in groundwater from the San Juan basin, New Mexico. Quarternary Res. 43, 209 220. Talma, A.S., Vogel, J.C. and Heaton, T.H.E. (1984) The geochemistry of the Uitenhage artesian aquifer (carbonate solution in a closed system). Isotope Hydrology in Water Resources Development 1983, IAEA Vienna, 481497. Tamers, M.A. and Scharpenseel, H.W. (1970) Sequential sampling of radiocarbon in groundwater. In: Isotope Hydrology 1970, IAEA, Vienna, 241257. *Todd, D.K. (1980) Groundwater Hydrology, 2nd ed. John Wiley, New York. Torgersen, T. and Clarke, W.B. (1985) Helium accumulation in groundwater, 1: An evaluation of sources and the continental ux of crustal 4He in the Great Artesian Basin, Australia. Geochim. et Cosmochim. Acta 49, 12111218. Toth, J. (1963) A theoretical analysis of groundwater ow in small drainage basins. J. Geophys. Res. 68, 47954812. Tremblay, J.J., DCruz, J. and Anger, H. (1973) Salt water intrusion in the Summerside area, P.E.I. Ground Water 11, 2127. Verhagen, B.Th., Mazor, E., and Sellschop, J.P.F. (1974) Radiocarbon and tritium evidence for direct recharge to groundwaters in the northern Kalahari. Nature 249, 643644. Verhagen, B.Th., Smith, P.E., McGeorge, I., and Dzimebowski, Z. (1979) Tritium proles in Kalahari sands as a measure of rain-water recharge. In: Isotope Hydrology 1978, IAEA, Vienna, 2, 733751. Vogel, J.C. (1970) Carbon-14 dating of groundwater. In: Isotope Hydrology 1970, IAEA, Vienna, 225239. Vogel, J.C. and Van Urk, H. (1975) Isotopic composition of groundwater in semiarid regions of southern Africa. J. of Hydrology, 25, 2336. Vogel, J.C., Thilo, L., and Van Dijken, M. (1974) Determination of groundwater recharge with tritium. J. of Hydrology 23, 131140. Vuataz, F.D. (1982) Hydrologie, geochimie et geothermie des eaux thermales de Suisse et des regions Alpines limitrophes. Materiaux pour la geologie de la Suissehydrologie No. 29. Kummerly & Frey Georgraphischer Verlag, Berne. *Walton, W.C. (1988) Groundwater Pumping Tests Design and Analysis. H.K. Lewis, London. Wilmoth, B.M. (1972) Salty groundwater and meteoric ushing of contaminated aquifers in West Virginia. Ground Water 10, 99105. Wilson, L.G. and DeCook, K.J. (1968) Field observations on changes in the subsurface water regime during inuent seepage in the Santa Cruz River. Water Resourc. Res. 4, 12191233. Winslow, J.D., Stewart, Jr., H.G., Johnston, R.H., and Crain, L.J. (1965) Groundwater resources of eastern Schenectudy County, New York, with emphasis on inltration from the Mohawk River. State of New York Conservation Department Water Resources Commission Bull. 57, 148.



Yurtsever, Y. and Payne, B.R. (1979) Application of environmental isotopes to groundwater investigation in Qatar. In: Isotope Hydrology 1978, IAEA, Vienna, 2, 465490. Zaikowsky A., Kosanke, B.J., and Hubbard, N. (1987) Noble gas composition of deep brines from the Palo Duro Basin, Texas. Geochim. et Cosmochim. Acta 51, 7384. Zartman, R.E., Wasserburg, G.J., and Reynolds, J.H. (1961) Helium, argon and carbon in some natural gases. J. Geophys. Res. 66, 277306.

Special Publications of the International Atomic Energy Agency P.O. Box 100, Vienna, Austria
Application of Isotope Techniques in Hydrology, 31 pp. 1962. Arid-Zone Hydrology: Investigations with Isotope Techniques, 265 pp., 1980. Concentration in Precipitation (19691983), vols. 17. Environmental Isotope Data No. 1: World Survey of Isotope Concentration in Precipitation (19691983), vols. 17. Interpretation of Environmental Isotope and Hydrochemical Data in Groundwater Hydrology, 228 pp., 1976. Isotopes in Hydrology, 740 pp., 1967. Isotope Hydrology 1978, vol. 1: 440 pp., vol. II: 540 pp., 1979. Isotope Hydrology 1983, 874 pp., 1984. Isotope Techniques in Hydrology, (Bibliography) vol. I: 18571965, 228 pp., 1968; vol. II: 19681971, 233 pp., 1973. Isotope Techniques in the Hydrological Assessment of Potential Sites for the Disposal of High-Level Radioactive Wastes, 164 pp., 1983. Isotope Techniques in the Study of the Hydrology of Fractured and Fissured Rocks, 306 pp., 1986. Nuclear Techniques in Groundwater Pollution Research, 286 pp., 1980. Paleoclimates and Paleowaters: A Collection of Environmental Isotope Studies, 216 pp., 1983. Stable Isotope Hydrology: Deuterium and Oxygen-18 in the Water Cycle, 339 pp., 1981. Statistical Treatment of Environmental Isotope Data in Precipitation, 276 pp., 1981. Tritium and Other Environmental Isotopes in the Hydrological Cycle, 83 pp., 1967.


Aerated zone, 13 Algeria, 201 Alkalinity, 176 Aquiclude, 18 Aquifer, 16 Artesian, 25, 243 Atomic weight, 99 Australia, 48, 148, 240, 262, 273, 277, 278, 280, 322 Baseow, 33, 36 Base of drainage, 32 Botswana, 144, 184, 234, 370, 374 Brazil, 200 Canada, 283 Carbon-14 dating 177, 231 Chile, 240 Chloride, sources, 149 Chlorine-36, 271 Compartmentalization, 39, 42, 128 Conned system, 24, 57

Connectivity, hydraulic, 38, 125, 127 CO2-induced reactions, 136, 151 Darcys experiment, 29 Data banks, 401 Data quality, 107 Dating, 28, 62, 216, 233, 271, 312, 316, 324 Denmark, 344 Depth proles, 160 Diagrams composition, 121, 122 ngerprint, 115,119 Discharge, 19, 89 Drilling, 9, 158 Drinking water, 392, 394 Education, 403 Eforescence, 178 Electrical conductivity, 172 Elements, 97 End-members, 132, 135



England, 256, 259, 262, 308, 319, 321, 324 Errors, 104, 111 Evaporation, 182 Evapotranspiration, 20, 150 Exhibitions, 407 Faults, 58 Filtering, 177 Fingerprint, 115, 119, Flow, 28, 31, 34, 75, 83 France, 226, 244, 246, 250 Geothermal, 42 Germany, 239, 363 Glacial, 306 Greece, 204, 207 Gypsum, 51, 145 Halite (rock salt), 51, 145, 274 Hawaii, 235 Helium, radiogenic, 312, 316 Historical data, 161 Hungary, 269 Hydraulic barriers, 40 Hydraulic connectivity, 38, 53, 61, 62, 125, 127 Hydrogen isotopes, 99 Impermeability, 21 India, 249, 251 Inltration, 35 Ions compounds, 101 conservative, 61 valences, 100 Irrigation, 389 Isotopes, 98 Isotopic water composition altitude effect, 194 amount effect, 190 continental effect, 193

[Isotopic water composition] temperature effect, 189 Israel, 103, 132, 134, 152, 159, 184, 207, 253, 265, 269, 292, 298, 302, 335 Italy, 198, 203, 226 Karst, 27, 267, 302 Laboratory, checking, 105 Land use map, 396 L-shaped groundwater ow model, 34 Meteoric water line, 185, 186 Mixing of waters, 6, 84, 107, 129, 132, 134, 145, 264, 320, 330 Models conceptual, 7 L-shape ow, 34 mathematical, 7 U-shape ow, 43, 45 Monitoring networks, 394, 399, 402 Multisampling, 206 Museums, 403, 406 Nigeria, 262 Nitrate, pollution, 343, 346 Noble gases, 178, 287, 290 Oxygen, dissolved, 174 Paleotemperature, 305, 328, 334 Permeability, 21, 22 Pesticide pollution, 348 Petroleum hydrology, 42 pressure, 42 pH, 173



Pollution, 166, 340 Porosity, 23 Pumping test, 77, 78, 161 Reaction error, 105, 112 Recharge, 19, 35, 72, 73, 84 Reports, 411 Reproducibility, 102, 107, 112 Rocks, 50 Saturated zone, 15 Sea-spray, 147 Seawater encroachment, 141 Smell, 171 South Africa, 198, 243 Stagnant aquifer, 27 Standards, 393 Subsidence basin, 30 Sustainable development, 376 Switzerland, 93, 143, 146, 225, 301 Taste, 171 Teaching, 403, 408 Temperature, 80, 82, 87, 172, 291, 297 Through-ow, 24, 35, 40 Time series, 10, 90, 93, 139, 162

Tritium, 177, 210, 216, 220, 229 Unconned system, 24, 34 USA, 84, 87, 141, 202, 262, 325, 346, 349, 350, 353, 356, 359, 360, 369 U-shaped groundwater ow model, 43, 45 Water composition, 1, 64, 138 cycle, 4 encoded information, 3 isotopic composition, 181 quality, 5, 50 Water-rock interaction, 136, 151, 237, 241 Water table, 15, 66, 68, 76, 126 Wells, observations, 14 Zones aerated, 13 lateral ow, 39 saturated, 15 stagnation, 36, 40 through-ow, 35, 40 vertical down ow, 37